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Preface

Aromatic rings are prevalent throughout nature, found in hydrocarbons,

nucleic acids, proteins, metabolites, and drugs. Aromatic groups are also
ubiquitous in materials science, where they are prized for their programmed
reactivity and chemical stability.1,2 The interactions of aromatic groups
with their surroundings are central to their properties and functions in all
of these settings. In this book we seek to introduce the reader to modern
research on aromatic interactions. This monograph should not be viewed
as a comprehensive review of all knowledge on aromatic systems, but rather
we aspire to highlight topics of current interest that have emerged in the last
several years. The scope of topics to be covered fits into three main catego-
ries, including: (i) new developments in our fundamental understanding of
aromatic interactions (substituent effects, electronic effects, thermodynam-
ics), (ii) discovery and characterization of new kinds of aromatic interactions
(anion–π interactions, aromatic interactions on surfaces), and (iii) emerging
applications of aromatic interactions (biological sciences, catalysis, organic
electronics, and materials science).
The field of aromatic interactions has generated significant new content,
and with it renewed controversy in recent years. The fundamental nature of
substituent effects in aromatic interactions has been discussed, the term
“π-stacking” itself has been reconsidered, the understanding of the nature of
the interaction between ions and aromatic rings continues to evolve, and new
theoretical frameworks have been developed and tested against experiment.
Against this backdrop of an evolving basic knowledge, aromatic interactions
have repeatedly appeared among the applied solutions found for problems
in biology and materials science.
While many other weak interactions have been well understood for
decades, our fundamental understanding of aromatic interactions has con-
tinued to evolve in the last 10 years. Early models for aromatic interactions

Monographs in Supramolecular Chemistry No. 20

Aromatic Interactions: Frontiers in Knowledge and Application
Edited by Darren W. Johnson and Fraser Hof
© The Royal Society of Chemistry 2017
Published by the Royal Society of Chemistry, www.rsc.org

v
 View Online

vi Preface
were based primarily on electrostatics; however, in order to explain the
observed strengths of interactions, van der Waals forces and desolva-
tion were also highlighted as playing significant energetic roles.3,4 When
dealing with polarized aromatic systems, the early model by Hunter and
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Sanders broke the electrostatic contributions down into πσ–πσ (present in non-
polarized systems), atom–atom (partial atomic charge attraction or repulsion),
and atom–πσ (the interaction of the partial atomic charge of one molecule with
the out-of-plane π electron cloud of another molecule). Such a model accu-
rately predicts the strengths of benzene dimer interactions, as well as ben-
zene–hexafluorobenzene, but breaks down with more complex systems.
Since this initial model, there have been many advances in understanding
the phenomenon of “aromatic interactions” through detailed physical organic
studies on solutions, solid-state investigations, and quantum mechanical
computations. Such an understanding has enabled the rational design of
new functional molecular systems relying on aromatic interactions.5 Stoddart
has made rotaxanes that depend on aromatic interactions to control molecu-
lar movements and locations;6 Sharpless has utilized host ligands that bind
aromatic guests in defined geometries that favor reactivity;7 organic materials
featuring π–π stacking are used in semiconducting charge-transfer materials,8
just to name a few. Practical advances like these have progressed in lockstep
with studies that reveal the fundamental nature of aromatic interactions.
Aromatic interactions remain a vibrant area of study because of their com-
plexity. This book dives into further theoretical understanding of the nature
of these interactions, with several chapters describing the latest approaches
to arene–arene, cation–π, anion–π, and main group lone pair–π interactions.
In Chapter 1, Lewis goes beyond the quadrupolar electrostatic distribution
of aromatic systems and brings in aromatic polarizability, induction, disper-
sion, exchange, and substituent-dominated effects to improve the under-
standing of aromatic interactions. The strength of the contributing factors,
as well as their individual contributions to the overall energy of the interac-
tion, are further discussed for simple arene–arene interactions as well as cat-
ion–π. And in Chapter 2, Maji and Wheeler expand on how this fundamental
understanding of aromatic interactions can be harnessed to direct organic
reactions with new organocatalysts.
The list of canonical types of aromatic interactions is still expanding. Since
the last publication of this Monographs series, anion–π (Chapters 2 and 3)
and main group–π (Chapter 4) interactions have entered the scene. The
strength of anion–π interactions is enhanced with an increase in electron
deficiency of the out-of-plane π electron cloud; however, the strength is also
increased by the anion’s ability to induce a dipole in the π-electron cloud.
Anion–π and related interactions have been found to be a powerful directing
effect for organic reactions, and catalysis, as mentioned in Chapter 2 and
highlighted in greater detail in Chapter 3. Harnessing the understanding
of anion–π interactions led Frontera and Ballester to propose that extended
π-systems should be used in anion–π complexes due to their increased
polarizability.
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Preface vii
Even more recently, main group element lone pair–π interactions have
been defined, characterized, and exploited for self-assembly (Chapter 4).
Many examples of such contacts have been discovered through searches of
the Cambridge Structural Database (CSD). Much like cation–π interactions,
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the polarizability of the participating electrons is key for the interaction to

take place. However, given the ambipolar-type nature of some main group
complexes, the main group element can in some cases donate its electron as
a π-base to a π-acidic aromatic ring, or alternately, serve as the Lewis acidic
cation in a cation–π complex, thereby exhibiting features of both anion–π
and cation–π interactions, sometimes even within the same complex.
Changes in the way the field has modeled aromatic interactions compu-
tationally, and the changes advanced by that understanding, are driven by
trying to accurately predict what is experimentally observed in solution. This
has driven work aimed at understanding how simple model systems can be
used for quantitative measurement and the study of non-covalent interac-
tions between aromatic rings in solution. In Chapter 5, Shimizu and Hwang
describe a series of such systems carefully designed to control and under-
stand different contributing factors such as electrostatics, dispersion, repul-
sion, and solvent effects. There are key challenges that must be overcome,
such as defining a system where other weak forces such as dipole effects, ste-
rics, and secondary interactions are not mistaken for aromatic interactions.
The models that have been studied vary from simple fixed interactions of
aromatics to adapting biomolecular frameworks for physical organic models.
The combinations of these studies, both simple and complex, have and
continue to contribute greatly to the fundamental understanding of these
interactions. Paired with computational studies and single crystal X-ray dif-
fraction, these solution state studies have benefitted biological understand-
ing and biomimetic design of molecular structures and systems.
The inspiration for using subtle aromatic interactions to direct and/or
catalyze organic reactions (Chapters 2 and 3) is derived in part from studying
biological systems. We devote two chapters to biological examples of aro-
matic interactions: in Chapter 6, Bockus and Urbach describe aromatic inter-
actions of amino acids and proteins; in Chapter 7, Koenig and Waters focus
on cation–π interactions in biological chemistry. Both chapters describe
efforts to understand the fundamental nature of interactions, while also
describing the progression to creating synthetic molecules that can bind to
and modulate natural, biological partners. A definitive fundamental lesson
highlighted in Chapter 7 explores the use of isosteric R-NMe3+ and R-C(Me)3
ligands to understand the role of cation–π interactions in natural protein–
protein interactions. Chapter 6 highlights a seminal example of the type of
synthetic recognition systems enabled by aromatic interactions in viologen-
bound hosts that co-encapsulate aromatic side chains of amino acids, pep-
tides, and whole proteins.
The principles that allow aromatic interactions to be utilized in molecular
systems have also advanced into the realm of materials chemistry. This
application in materials chemistry can take on different forms: aromatic
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viii Preface
interactions can be used for functionalizing materials surfaces, molecular
receptors can be applied to a surface, and favorable interactions with the
surface can help facilitate organized self-assembly on the surface.8–10 Apply-
ing aromatic molecules to metallic surfaces has afforded new characteriza-
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tion methods, as well as novel reactivity. In Chapter 8, Marangoni, Cloke and

Fischer introduce such surface characterization methods, with a focus on the
techniques that allow visualization at submolecular resolution. These meth-
ods are powerful tools in advancing the understanding of aromatic mole-
cules and their interactions. The metallic substrates can also be utilized to
control reactivity of the adsorbed aromatic compounds, including reactions
that are unprecedented in the solution phase. By “building up” complexity
on the surface, the creation of 2D and 3D molecules is now possible. This
further advances extended π surfaces, with promise for improved electronic
devices such as organic light emitting diodes, organic thin film transistors,
and organic photovoltaics.
Structural investigations of aromatic molecules on crystalline surfaces has
resulted in novel reactivity and new applications in materials chemistry. The
designed use of predictive aromatic interactions has impacted fields ranging
from catalysis (through conformational control), drug design (molecular
recognition), and materials chemistry (surface functionalization), among
others. Such designs would not be possible without the continued evolu-
tion of fundamental understandings furthered by computational chemistry
informed by solution-state models—both synthetic and biological—as well
as data from solid state structural investigations.
As can be seen from the content described above, this book does not aim
to be a tutorial review on aromatic interactions. We have aimed instead to
include content that describes the last 10 years of progress—the newest
classes of interactions, latest ways of understanding interactions, and the
cutting edge of experimental systems that exploit this knowledge to drive
new science. It is clear that the field of Aromatic Interactions is not yet
settled. We look forward to the next decade of discovery.
Kara M. Nell, University of Oregon, Eugene, USA
Fraser Hof, University of Victoria, Victoria, Canada
Darren W. Johnson, University of Oregon, Eugene, USA

References
1. K. A. Wilson, J. L. Kellie and S. D. Wetmore, Nucleic Acids Res., 2014, 10,
6726–6741.
2. C. A. Hunter, J. Mol. Biol., 1993, 230, 1025–1053.
3. C. A. Hunter and J. K. M. Sanders, J. Am. Chem. Soc., 1990, 112, 5525–5534.
4. C. A. Hunter, Chem. Soc. Rev., 1994, 23, 101–109.
5. C. A. Hunter, K. R. Lawson, J. Perkins and C. J. Urch, J. Chem. Soc., Perkin
Trans. 2, 2001, 651–669.
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Preface ix
6. R. A. Bissell, E. Cordova, A. E. Kaifer and J. F. Stoddart, Nature, 1994, 369,
133.
7. M. R. Bryce, Adv. Mater, 1999, 11, 11.
8. H. C. Kolb, P. G. Andersson and K. B. Sharpless, J. Am. Chem. Soc., 1994,
Published on 15 November 2016 on http://pubs.rsc.org | doi:10.1039/9781782626626-FP005

116, 1278.
9. K. M. Nell, S. A. Fontenot, T. G. Carter, M. G. Warner, C. L. Warner, R. S.
Addleman and D. W. Johnson, Environ. Sci.: Nano, 2016, 3, 138–145.
10. S. Lee, B. E. Hirsch, Y. Liu, J. R. Dobscha, D. W. Burke, S. L. Tait and A. H.
Flood, Chem.–Eur. J., 2016, 22, 560–569.
Published on 15 November 2016 on http://pubs.rsc.org | doi:10.1039/9781782626626-FP011

Contents

Chapter 1 Modern Computational Approaches to Understanding

Interactions of Aromatics  1
Michael Lewis, Christina Bagwill, Laura Hardebeck
and Selina Wireduaah

1.1 I ntroduction and Background  1

1.1.1 Arene–Arene Interactions  2
1.1.2 Cation–Arene Interactions  3
1.1.3 Beyond the Aromatic Quadrupole Moment  4
1.2 Computational Approaches to Understanding
Arene–Arene Interactions  5
1.2.1 The Nature of Arene–Arene Interactions  5
1.2.2 Predicting the Strength of Arene–Arene
Interactions  9
1.3 Computational Approaches to Understanding
Cation–Arene Interactions  10
1.3.1 The Nature of Cation–Arene Interactions  10
1.3.2 Predicting the Strength of Cation–Arene
Interactions  13
1.4 Summary  14
References  15

Chapter 2 Role of Aromatic Interactions in Directing Organic

Reactions  18
Rajat Maji and Steven E. Wheeler

2.1 I ntroduction and Background  18

2.2 Aromatic Interactions of Relevance to Organic
Reactions  19

Monographs in Supramolecular Chemistry No. 20

Aromatic Interactions: Frontiers in Knowledge and Application
Edited by Darren W. Johnson and Fraser Hof
© The Royal Society of Chemistry 2017
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xi
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xii Contents
2.3 A romatic Interactions in Non-Catalytic Reactions  22
2.4 Aromatic Interactions in Transition-Metal
Catalyzed Reactions  24
2.5 Aromatic Interactions in Organocatalysis  25
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2.6 Aromatic Interactions in Cooperative Catalysis  31

2.7 Reactions Directed by Anion–π Interactions  31
2.8 Reactions Directed by π–π+ Interactions  33
2.9 Concluding Remarks  34
Acknowledgements  34
References  34

Chapter 3 Anion–π Interactions: Theoretical Studies,

Supramolecular Chemistry and Catalysis  39
A. Frontera and P. Ballester

3.1 I ntroduction  39
3.2 Physical Nature  41
3.3 Anion–π Interactions in Solution  46
3.3.1 Supramolecular Chemistry and Synthetic
Receptors Involving Anion–π Interactions  46
3.3.2 Anion–π Interactions in Reaction Catalysis  65
3.3.3 Ionic Liquids  74
3.4 On the Importance of Anion–π Interactions in
the Solid State  76
3.4.1 Charge Neutral π-Systems  76
3.4.2 Aromatic Ligands Coordinated to Metal Ions  83
3.4.3 Positively Charged or Protonated Aromatics  86
3.5 Outlook  88
Acknowledgements  88
References  89

Chapter 4 A New Non-Covalent Bonding Mode in Supramolecular

Chemistry: Main Group Element Lone-Pair–π(arene)
Interactions  98
Ignez Caracelli, Ionel Haiduc, Julio Zukerman-Schpector and
Edward R. T. Tiekink

4.1 I ntroduction  98
4.2 Methodology  100
4.3 Overview of M(lp)⋯π(arene) Interactions  102
4.3.1 Indium(i)  102
4.3.2 Thallium(i)  102
4.3.3 Tin(ii)  104
4.3.4 Lead(ii)  105
4.3.5 Arsenic(iii)  106
4.3.6 Antimony(iii)  108
4.3.7 Bismuth(iii)  108
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Contents xiii
4.3.8 Selenium(ii, iv)  109
4.3.9 Tellurium(ii, iv)  115
4.4 Biological Relevance  116
4.5 Conclusions and Outlook  118
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Acknowledgements  119
References  119

Chapter 5 Solution-Phase Measurements of Aromatic Interactions  124

K. D. Shimizu, P. Li and J. Hwang

5.1 I ntroduction  124

5.2 Types of Model Systems  125
5.2.1 Bimolecular Model Systems  125
5.2.2 Unimolecular Model System  126
5.2.3 Thermodynamic Approach  126
5.2.4 Kinetic Approach  127
5.2.5 Analysis of Experiment Models  127
5.2.6 Isolation of the Interaction Energy  128
5.3 Case Studies of Solution-Phase Measurements
of Aromatic Interactions  129
5.3.1 Aromatic Stacking Interactions  129
5.3.2 Aromatic Edge-to-Face Interactions  140
5.3.3 Aliphatic CH–π Interactions  145
5.3.4 Aromatic Cation–π Interactions  150
5.3.5 Anion–π Interaction  155
5.3.6 Lone Pair–π Interaction  159
5.4 Conclusion  162
Acknowledgements  163
References  163

Chapter 6 Molecular Recognition of Aromatic Peptides and

Proteins in Nature and by Design  172
Andrew T. Bockus and Adam R. Urbach

6.1 Overview  172

6.2  romatic Amino Acids 
A 173
6.3 Aromatic Residues in Biological Complexes  175
6.4 Designed Ligands  180
6.5 Efficiency of Aromatic Residues  182
6.6 Synthetic Receptors  183
6.7 Synthetic Receptors for Amino Acids  184
6.7.1 Aromatic Amino Acid Recognition by
Viologen-Containing Receptors  184
6.7.2 Aromatic Amino Acid Recognition by
Cyclodextrins  186
6.7.3 Aromatic Amino Acid Recognition by
Cucurbiturils  188
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xiv Contents
6.7.4 R
 ecognition of Non-Aromatic Amino
Acids by Synthetic Receptors  189
6.8 Recognition of Aromatic Peptides by Synthetic
Receptors  192
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6.8.1 Early Receptors for Peptides  193

6.8.2 Peptide Recognition by Coordination
Complexes  195
6.8.3 Peptide Recognition by Cucurbit[n]urils  197
6.9 Recognition of Aromatic Sites on Proteins by
Synthetic Receptors  203
6.10 Lessons Learned and Challenges  206
Acknowledgements  208
References  208

Chapter 7 Cation–π Interactions in Biomolecular Recognition  214

Amber L. Koenig and Marcey L. Waters

7.1 T he Nature of the Cation–π Interaction  214

7.2 Model Systems for Cation–π Interactions in
Aqueous Solution  216
7.2.1 Applications of Synthetic Systems that
Mediate Cation–π Interactions  218
7.3 Cation–π Interactions in Proteins  218
7.4 Cation–π Interactions in Nucleic Acids  225
7.5 Cation–π Interactions in Lipids  229
7.6 Conclusions  232
References  232

Chapter 8 Aromatic Molecules on Metallic Surfaces: Structure and

Reactivity  238
Tomas Marangoni, Ryan R. Cloke and Felix R. Fischer

8.1 I ntroduction  238

8.2 Structural Investigations of Aromatic Molecules
on Surfaces  240
8.2.1 General Surface Characterization Techniques  240
8.2.2 Visualization Techniques with Sub-Molecular
Resolution: STHM and nc-AFM  241
8.3 Reactivity of Aromatic Molecules on Metallic
Surfaces  247
8.3.1 Surface-Mediated Polymerization  248
8.3.2 Cyclodehydrogenation Reactions  255
8.3.3 Metal-Coordination Reactions  257
8.3.4 Graphene Nanoribbon Synthesis  261
8.4 Conclusions  269
References  269
Subject Index  277
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Chapter 1

Modern Computational
Approaches to Understanding
Interactions of Aromatics
Michael Lewis*a, Christina Bagwilla, Laura
Hardebecka and Selina Wireduaaha
a
Department of Chemistry, Saint Louis University, 3501 Laclede Avenue,
Saint Louis, Missouri, 63103, USA
*E-mail: [email protected]

1.1 Introduction and Background

Two of the most common, and widely studied, interactions of aromatics are
arene–arene and cation–arene interactions1 and this chapter will focus on
modern computational approaches aimed at understanding them. Two aro-
matic molecules generally interact to form one of the conformations shown
in Figure 1.1(a): parallel face-to-face (pff), offset face-to-face (osff), edge-to-
face (etf), or t-shaped (tsh).2,3 Of course, each one of these conformations has
an infinite number of possible structures, largely dependent on the angle
between the planes of the aromatic rings, and the degree to which the mole-
cules are offset. Cation–arene interaction4 normally assume a conformation
where the cation is over the π-density of the aromatic ring, as shown in Figure
1.1(b), and this has led to the interaction being termed cation–π. Depending
on the nature of the aromatic, the cation may assume a position not directly

Monographs in Supramolecular Chemistry No. 20

Aromatic Interactions: Frontiers in Knowledge and Application
Edited by Darren W. Johnson and Fraser Hof
© The Royal Society of Chemistry 2017
Published by the Royal Society of Chemistry, www.rsc.org

1
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2 Chapter 1
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Figure 1.1 
General conformations of: (a) arene–arene interactions; (b) cation–
arene interactions.

above the center of the aromatic, and for certain polar aromatics the most
stable cation–arene conformation has the cation binding to the negative end
of the molecular dipole.5
A brief historical background on each of these interactions, largely focused
on computational investigations, is given below, and this is followed by a
review of current computational work aimed at understanding the nature of
the interactions and predicting the strength of the interactions.

1.1.1 Arene–Arene Interactions

In the mid-1980s, Burley and Petsko reported one of the seminal studies
showing that arene–arene interactions were distinct from typical hydropho-
bic interactions, showing that aromatic amino acid residues are predomi-
nantly found in the vicinity of other aromatic amino acid residues, and that
the residues interact in an energetically favorable manner.6 Subsequently,
non-covalent interactions of aromatics have been shown to play a significant
role in a wide range of biologically and chemically relevant systems and pro-
cesses. Face-to-face arene–arene interactions are important in nucleic acid
structure1,7 and aromatic interactions are important in carbohydrate inter-
actions8,9 the structure of helical peptides10 aromatic amino acid interac-
tions,11 DNA/RNA protein complexes12 biological receptor interactions13 and
peptide formation.14 In addition, due to the ubiquity of aromatics in biolog-
ical systems, aromatic interactions are often a focus in drug development,
and many pharmaceuticals contain an aromatic moiety.15 In terms of chem-
ical systems, a few areas where aromatic interactions have been shown to
be important include molecular recognition1,16 supramolecular complexes17
molecular self-assembly18 nanomaterials19 and organic catalysis.20,21
Early computational investigations aimed at understanding arene–arene
interactions focused on the aromatic quadrupole moment.22 Figure 1.2(a)
presents a pictorial view of the quadrupole moments of benzene and hexa-
fluorobenzene. Benzene has a negative quadrupole moment23 and this can
be viewed as the π-electron density region being more electron-rich than the
hydrocarbon σ-framework region. Conversely, hexafluorobenzene has a pos-
itive quadrupole moment23 and the hydrocarbon σ-framework region with
the fluorine atoms is more electron-rich than the π-electron region. Hunter
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Modern Computational Approaches to Understanding Interactions of Aromatics 3

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Figure 1.2  The quadrupole moments of benzene (negative; −8.7 ± 0.5 DÅ) and
(a)
hexafluorobenzene (positive; +9.5 ± 0.5 DÅ) are opposite in sign.23 (b) The
preferred etf and osff conformations of C6H6–C6H6 complexes, and the
preferred pff conformations of C6H6–C6F6 complexes, can be explained
via the aromatic quadrupole moments.

and Sanders discussed the nature of π–π interactions through a charge distri-
bution model2 the results of which dictate that two aromatics with the same
quadrupole moment, such as benzene, would interact most favorably either
by adopting an etf or tsh conformation or by having the negative ends of their
quadrupole moments get out of each other’s way via an osff conformation
(Figure 1.2(b)). Conversely, aromatics that have quadrupole moments oppo-
site in sign, such as benzene and hexafluorobenzene, would be expected to
prefer the pff conformation (Figure 1.2(b)), and this was demonstrated in the
solid state24 and via computations.25

1.1.2 Cation–Arene Interactions

Kebarle and coworkers first reported the importance of the cation–arene
interaction when they showed that the K+-benzene dimer had slightly more
binding ΔH and ΔG° values than the K+-water dimer in the gas phase.26 The
result was quite surprising at the time, as it suggests a cation would prefer
to bind to a nonpolar molecule, benzene, rather than the highly polar water
molecule. Kebarle and coworkers suggested the cation–π conformation
shown in Figure 1.1(b) to explain why the cation would be attracted to an
aromatic ring. Subsequently, cation–π interactions have been shown to be
important in a wide range of chemistry and biology1 with significant early
work being performed by the Dougherty group.27
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4 Chapter 1
Similar to their work on the importance of arene–arene interactions in
protein structures, Burley and Petsko also showed that amino acid residues
with cationic side chains are preferentially found in the vicinity of aromatic
amino acids.28 In addition to being important in protein stability, notable
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areas where cation–π interactions have been shown to be important in biol-

ogy include enzyme/protein-substrate recognition29,30 and ion-transport pro-
cesses.31 In chemistry, cation–π interactions have been reported to play a role
in organic reaction development32 and in nanomaterials.19
As was the case for arene–arene interactions, early computational work
aimed at understanding cation–π interactions focused on the aromatic
quadrupole moment.33 In general, cation–arene interactions were generally
investigated for electron-rich aromatics, which have negative quadrupole
moments (i.e., benzene23), and the interaction can be described as a positive
charge being attracted to the negative region of the arene quadrupole. Fig-
ure 1.3 shows this for Na+-benzene. Related to understanding the cation–π
interaction via the aromatic quadrupole moment, early computational stud-
ies also aimed to understand the interactions via the aromatic electrostatic
potential, as reported by Dougherty and coworkers.27,34

1.1.3 Beyond the Aromatic Quadrupole Moment

The aromatic quadrupole moment proved useful as a model for predicting
some aspects of the interactions of aromatics. As discussed above, it can
be used to understand the preferred conformations for benzene–benzene
and benzene–hexafluorobenzene dimers. In addition, it provides a good
approach for understanding the cation–arene interactions of electron-rich
aromatics such as benzene. However, the quadrupole moment describes the
aromatic electron density distribution, and using it to describe arene–arene
and cation–arene interactions suggests they can be understood in purely
electronic/electrostatic terms. Recent computational approaches to under-
standing interactions of aromatics have highlighted the importance of aro-
matic polarizability, the importance of forces other than electrostatics such
as induction, dispersion, and exchange, as well as substituent–substituent
and ion–substituent effects. The findings of these modern computational
approaches are discussed below, both in terms of understanding the inter-
actions and in terms of predicting the relative strength of the interactions.

Figure 1.3 
Prototypical cation–π complex of an aromatic: Na+–C6H6. The attraction
can be understood as the cation binding to the negative region of the
aromatic quadrupole moment.
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Modern Computational Approaches to Understanding Interactions of Aromatics 5

1.2  omputational Approaches to Understanding

C
Arene–Arene Interactions
1.2.1 The Nature of Arene–Arene Interactions
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Following the early computational work of Hunter and Sanders focusing on

the importance of the aromatic quadrupole moment in arene–arene inter-
actions2 many small-molecule models were experimentally investigated
to determine the forces important in arene–arene interactions35–39. The
small-molecule models generally focused on the interactions between substi-
tuted benzenes, and one such example is the 1,8-diarylnaphthalenes investi-
gated by Cozzi and Siegel (Figure 1.4).38,39 A common theme among this body
of work is the reported relationship between the experimentally determined
arene–arene binding energies and Hammett substituent constants, and the
interpretation that this correlation suggested the interactions were due to
polar/π electronic effects.
At the same time as experimental work showing correlations between
arene–arene binding energies and Hammett constants continued to be
reported1 some experimental results began to appear suggesting forces other
than electronic/electrostatic effects were important in understanding the
nature of arene–arene interactions. Gung and coworkers showed that when
one aromatic was electron-rich and the other aromatic was electron-poor
(i.e., hexafluorobenzene), the experimentally measured arene–arene binding
energies did not correlate with the Hammett constants, and they suggested
charge-transfer effects may be important in such arene–arene interactions.40
In addition to these results, the early 2000s saw the beginning of a wealth of
computational results showing there was no general relationship between
arene–arene binding energies and Hammett constants, and suggesting that
forces other than electronic/electrostatic effects were important in under-
standing the nature of these interactions. Primary among these studies was
the work of Sherrill and coworkers employing the energy decomposition
method symmetry adapted perturbation theory (SAPT). The SAPT method41,42

Figure 1.4 
The 1,8-diarylnaphthalenes system is an example of a small-mole-
cule model used to experimentally investigate arene–arene binding
energies.38,39
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6 Chapter 1
allows for the overall non-covalent binding energy Ebind to be broken down
to the energies due to electrostatics (Eele), induction (Eind), dispersion (Edisp),
and exchange (Eexch). Using the SAPT method to investigate mono-substituted
benzene–benzene dimers, Sherrill’s research group showed the energy due
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to dispersion (Edisp) is a greater contributor to the overall Ebind value than Eele
for both pff and etf conformations.43 This result was also reported by Tsuzuki
and coworker44 using a different computational approach to determine Eele,
Eind, and Edisp; they calculated Eele and Eind using the program ORIENT,45 while
Edisp was approximated as the energy contribution from electron correlation
(Ecorr) on Ebind. Tsuzuki and coworkers determined the Ecorr value as the dif-
ference between the interaction energies calculated with electron-correlated
levels and at the HF levels.44 The Tsuzuki group computationally investigated
arene–arene interactions in pff, and various etf, tsh, and osff conformations
when two electron-rich aromatics were interacting (toluene–toluene, tolu-
ene–benzene)46 when two electron-poor aromatics were interacting (nitro-
benzene–nitrobenzene)47 and when an electron-rich and electron-poor
aromatic were interacting (nitrobenzene–benzene47 and hexafluorobenzene–
benzene48), and in all cases they found Edisp was the greatest contributor to
Ebind. Kim and coworkers studied tsh mono-substituted benzene–benzene
dimers where the substituted benzene could be either the vertical (Figure
1.5(a)) or horizontal (Figure 1.5(b)) aromatic in the dimer conformation.49
Using SAPT calculations they showed that Edisp was the greatest contributor
to Ebind regardless of the substituent or conformation. The examples from the
Sherrill, Tsuzuki, and Kim research groups capture the beginning of using
energy decomposition methods in computational chemistry to understand
interactions of aromatics broadly, and arene–arene interactions in particular.
The work provided the important insight that the energy due to electrostatics
(Eele) is not the major contributor to arene–arene binding energies (Ebind), and
the use of energy decomposition methods continues to be important in mod-
ern computational approaches to understanding arene–arene interactions.
The fact that SAPT calculations showed Edisp to be the major contributor to
Ebind values for arene–arene interactions suggested that Hammett constants

Figure 1.5 
Arene–arene dimers between a substituted benzene and benzene, and
in the t-shaped (tsh) conformation, can adopt two general conforma-
tions: (a) the substituted aromatic vertical; (b) the substituted aromatic
horizontal.
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Modern Computational Approaches to Understanding Interactions of Aromatics 7

should not correlate to arene–arene binding energies, as was reported in
most of the experimental work. Consistent with the emerging view from
computational work that Edisp was important to understanding arene–arene
interactions, Sherrill and coworkers showed that adding any substituent to
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one of the aromatics in a pff benzene–benzene dimer, regardless of whether

the substituent is electron-withdrawing or electron-donating, led to the
dimer having a stronger binding energy.43,50 A natural outcome of this result
is that Ebind values for substituted benzene–benzene dimers cannot correlate
with Hammett substituent constants, and Sherrill and coworkers explicitly
demonstrated this by computationally investigating pff substituted benzene–
benzene dimers with an approximately equal number of electron-withdrawing
(positive Hammett value) or electron-donating (negative Hammett value)
groups.51 The resulting graph of Ebind versus Σσm (multi-substituted benzenes
were investigated, and thus Σσm was used) yielded a parabola; there was no
linear correlation. Work by the Sherrill group43 and Kim group49 showed the
same trend is not apparent for tsh substituted benzene–benzene dimers, and
adding a substituent may make such a complex more or less binding than
the parent tsh benzene–benzene dimer, depending on the conformation.
Further investigating pff substituted benzene–benzene dimers using SAPT
calculations, Lewis and coworkers reported that adding any substituent to
the substituted aromatic results in a more binding Eele value.52 This surpris-
ing result was explained by the Sherrill group as being the result of charge
penetration.53 The equilibrium distances for most arene–arene dimers,
approximately 3.5–4.0 Å, brings the two aromatic monomers close enough
such that the electron density of one aromatic monomer electrostatically
interacts with the nuclei of the other aromatic monomer, and this is termed
charge penetration. Replacing a hydrogen atom with any substituent results
in a more electropositive nuclei, and increased electron density, thus increas-
ing the electrostatic attraction due to charge penetration.
Just prior to the reports from the Sherrill and Lewis groups, Houk and
Wheeler reported that the difference in substituted benzene–benzene pff dimer
binding energies was due to the substituent of the substituted benzene inter-
acting with the adjacent benzene ring, and not due to the substituent tuning
the electrostatics of the substituted benzene.54 Houk and Wheeler computa-
tionally demonstrated this important finding by comparing C6H5X–C6H6 Ebind
values to the Ebind values of HX–C6H6 dimers where the X group in HX and the
C6H5X mono-substituted benzene are the same (Figure 1.6). This comparison
showed that the difference in Ebind values between the C6H5X–C6H6 dimers for
various substituted benzenes (C6H5X) was the same as the Ebind differences for
HX–C6H6 dimers with various HX. This supports the notion that the strength
of substituted benzene–benzene interactions is dictated by the interaction
between the substituent and the adjacent (unsubstituted) benzene ring.54 This
finding aligns very well with the role of charge penetration in arene–arene
interactions.53 Houk and Wheeler expanded their work to etf dimers, compu-
tationally demonstrating the importance of substituents interacting directly
with the adjacent ring in understanding the nature of the interactions.3
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8 Chapter 1
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Figure 1.6 
The Ebind values for C6H5X–C6H6 pff dimers (a) can be approximated
very well as the Ebind values for HX–C6H6 complexes (b) where the X sub-
stituents in C6H5X and HX are the same. This supports the notion that
the strength of substituted benzene–benzene interactions are dictated
by the interaction between the substituent and the adjacent benzene
ring.54

Figure 1.7  Ebind values for C6H5X–C6H6 pff dimers (a) can be approximated very
The
well as the Ebind values for HX–C3H6 complexes (b) where the X substit-
uents in C6H5X and HX are the same. This supports the hypothesis that
arene–arene interactions are best understood as local, through-space,
interactions between proximal regions of the adjacent aromatics.55

Further computational work by Wheeler showed that arene–arene interac-

tions can be understood via direct local interaction between the substituent
and the region of the adjacent aromatic closest to the substituent (Figure
1.7).55,56 For instance, the Ebind values for C6H5X–C6H6 interactions correlated
very well with the Ebind values for HX–C3H6 dimers55 supporting the idea that
arene–arene interactions are best understood as local, through-space, inter-
actions between proximal regions of the adjacent aromatics. Wheeler has
also looked at the interactions of substituted benzenes with aromatics other
than benzene, such as borazine and 1,3,5-triazine, and computationally
demonstrated more generally that arene–arene interactions are best under-
stood as through-space interactions between the substituents of the substi-
tuted benzene with the proximal region of the neighboring aromatic, be it
benzene, borazine or 1,3,5-triazine.57
The recent advances in understanding arene–arene interactions under-
score the notion that the term “π-stacking” has become outdated, and
Martinez and Iverson highlighted this point a few years ago in an import-
ant perspective.58 In this work they point out the emerging importance of
considering direct interactions between substituents on the interacting
rings in understanding arene–arene complexes. In the four years since they
published their perspective, work by the Sherrill group and by Houk and
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Modern Computational Approaches to Understanding Interactions of Aromatics 9

Wheeler, among others, has cemented the idea that understanding arene–
arene interactions should not be approached from the lens of π–π stacking.
Rather, while arene–arene interactions were initially understood in terms of
the aromatic quadrupole moment, according to the Hunter–Sanders model,2
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modern computational approaches have shown the nature of these interac-

tions are best understood via the substituents on one aromatic monomer
interacting, through-space, with the proximal region of the adjacent aro-
matic monomer.56 Furthermore, the attractive nature of arene–arene dimers
can be understood as arising from charge penetration.53

1.2.2 Predicting the Strength of Arene–Arene Interactions

As described in various places throughout Section 1.2.1, a common theme in
computational work aimed at understanding the nature of arene–arene inter-
actions is correlating the Ebind values with physicochemical parameters, the
most common being Hammett substituent constants.59 While early experi-
mental work showed that Hammett values, usually σp38,39 correlated well with
the Ebind values, computational work showed the correlations deteriorated
when electron-donating substituents (with negative Hammett values) were
included in the analysis.51 Recent computational work by the Sherrill and
Wheeler groups, respectively noting the importance of charge penetration in
arene–arene interactions, and how the proximally close regions of the aro-
matics in an arene–arene dimer interact in a local, through-space manner,
demonstrates the complexity of the interactions and suggests the Ebind val-
ues should not correlate with an electronic parameter such as the Hammett
substituent constant. Not surprisingly, Sherrill and coworkers found the best
approach to correlating the Ebind values for tsh benzene-substituted benzene
dimers was with a multi-variable equation.60 The parameters included in
the equation were the Hammett σm, the molecular polarizability, and a term
accounting for the interaction between the substituents on one arene and
the H-atoms on the adjacent aromatic.60 Lewis and coworkers performed
SAPT calculations on a large set of substituted benzene–benzene dimers in
the pff conformation, and they found that most of the variability in Ebind was
due to variability in the energy due to electrostatics; the Eele term.52 The sum
of the non-electrostatic terms (Eind + Edisp + Eexch) was approximately constant
regardless of the substitution pattern of the substituted aromatic. Still, the
Ebind values did not correlate very well with the Hammett constants, and they
too employed a multi-variable equation to best correlate the Ebind values; the
terms in the equation were the Hammett constant σm and the molecular
polarizability parameter Mr.52
It is worth noting that modern approaches to predicting the strength of
arene–arene interactions are in line with Iverson’s suggestion58 that the terms
“π-stacking” and “π–π interactions” do not convey the important forces at
play in arene–arene binding. Both the Sherrill group60 and Lewis group52
have shown the need for multi-parameter equations to accurately predict the
strength of arene–arene interactions involving substituted benzenes, and the
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10 Chapter 1
Sherrill group explicitly uses a parameter that accounts for the interaction
between the substituents on one arene and the H-atoms on the adjacent aro-
matic.60 That the strength of arene–arene interactions involving substituted
benzenes cannot simply be predicted via Hammett constants strongly sug-
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gests that the terms “π-stacking” and “π–π interactions” are, as Iverson sug-
gests, outdated.58

1.3  omputational Approaches to Understanding

C
Cation–Arene Interactions
1.3.1 The Nature of Cation–Arene Interactions
As noted in the Introduction, Section 1.1.2, early work on understanding cat-
ion–π interactions of aromatics centered around the aromatic quadrupole
moment33 and the aromatic electrostatic potential (ESP).33,34 Dougherty and
coworkers showed that the total cation-binding energy, Ebind, of a cation and
negative quadrupole moment (Θzz) substituted aromatics correlates very well
with the ESP of the substituted aromatic.34 At about the beginning of the
2000s work by Cubero and coworkers61 and Tsuzuki and coworkers62 was dis-
seminated showing the importance of π-electron polarizability in cation–π
interactions. In both cases the groups demonstrated that cations induce
polarization in the aromatic compound (Figure 1.8), and this induction con-
tributes to the overall cation–π Ebind.
Shortly after the work illustrating the importance of π-electron polarizabil-
ity in cation–π interactions, computational results were reported showing
that positive Θzz aromatics bind cations63 however, this was initially described
as an anomaly due to the investigated aromatics having small positive Θzz
values. Not long after, Lewis and Clements demonstrated that substituted
aromatics with non-negligible positive Θzz values did bind cations.64 This
suggests that even though electrostatics is an important factor when describ-
ing the nature of cation–π interactions, other factors may also play import-
ant roles in the binding. The work of Cubero61 and Tsuzuki62 suggesting the
importance of π-electron density polarizability in cation–π interactions of
aromatics was offered as an explanation for why positive Θzz aromatics bind
cations.

Figure 1.8 
Work by Cubero and coworkers61 and Tsuzuki and coworkers62 suggested
cations induce polarization in the aromatic compound, and this induc-
tion leads to an increase in the cation–π Ebind.
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Modern Computational Approaches to Understanding Interactions of Aromatics 11

The results reported by Lewis and Clements suggested cation–π interac-
tions may, at least partially, be guided by direct interactions between the cat-
ion and the aromatic ring substituents,64 and this idea has been expanded
by Wheeler and Houk. In a similar fashion to their work demonstrating the
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importance of through-space interactions on arene–arene complexes (Fig-

ures 1.6 and 1.7), Wheeler and Houk showed that the Ebind value for a cat-
ion interacting with a substituted aromatic was reasonably approximated by
adding the Ebind values for a cation interacting with benzene and the Ebind
value of the cation interacting with the appropriate H–X.65 They also included
the Ebind value for the cation interacting with the H atoms of the substituted
benzene, and an equation illustrating the relationship is shown in Figure
1.9.65 This strongly suggests the Ebind values for cation–π interactions of sub-
stituted aromatics are dictated by through-space interactions between the
cation and aromatic substituents, rather than being dictated by the substit-
uents tuning the π-density of the aromatic ring. Suresh and Sayyed, taking
a somewhat similar approach to Wheeler and Houk, looked at how cations
interacted with different fragments of substituted aromatics and found that
through-space cation–substituent interactions were most important for elec-
tron-withdrawing substituents.66
Recent computational work by Quinonero and coworkers suggests that
cation–π interactions of aromatics are not entirely due to through-space
interactions between the cation and the aromatic substituents.67 Using the
calculated quadrupole moment to approximate the energy due to electrostat-
ics and the calculated dipole polarizabilities to approximate the energy due
to polarizability, Quinonero and coworkers found the cation–π binding ener-
gies of 104 substituted benzenes and 67 heteroaromatics were best described
by a combination of the electrostatic and polarizability parameters.67 The
dependence of the overall cation–π non-covalent binding energy on the aro-
matic dipole polarizabilities was interpreted by the authors as supporting the
notion that π-electron cloud polarizability was important in cation–π bind-
ing energies, and the interactions weren’t completely dictated by through-
space interactions between the cation and the aromatic substituents. The
authors concede that the polarizability term may reflect the polarizability

Figure 1.9 
The Ebind value for a cation interacting with a substituted aromatic
(C6H5X) can be reasonably approximated by adding the Ebind value for a
cation interacting with benzene, the Ebind value of the cation interacting
with the appropriate H–X, and the Ebind value for the cation interacting
with the H atoms of the substituted benzene.65
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12 Chapter 1
of the substituent in a through-space interaction; however, they show that
the polarizability of the C atom at the para position of the mono-substituted
benzenes correlates very well with the Hammett constant, σp, of the substit-
uent, but not σm. Quinonero and coworkers suggest this supports the notion
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that the substituents are directly involved in the polarization of the aromatic
ring, and that π-cloud polarizability and through-space interactions are both
important in the cation–π interactions of aromatics.67
Recent work by Lewis and coworkers68 and by Sastry and coworkers69
applied energy decomposition methods to understand the cation–π binding
of aromatics. Lewis and coworkers employed the SAPT approach with the
CCSD/­6-311++G** method and basis set to investigate the cation–π bind-
ing of substituted benzenes68 and Sastry and coworkers employed both the
reduced variational space (RVS) and the DFT-SAPT approaches to investigate
the energy decomposition of cation–π complexes involving benzene, phenol,
and a variety of heteroaromatics.69 As noted above in the arene–arene sec-
tion, the SAPT calculations allow for the total non-covalent binding energy
to be decomposed into Eele, Edisp, Eind, and Eexch, and the results reported by
Lewis and coworkers show that Eele is the largest contributor to the overall
cation–π binding of substituted benzenes. Furthermore, among the compo-
nent energy terms, Eele is most sensitive to the distance between the cation
and aromatic ring.68 The RVS method decomposes the overall non-covalent
binding energy into Eele, Eexch, Epol, and ECT, where Eele and Eexch are the same
as for the SAPT method, Epol is the energy due to polarization, and ECT is
the energy due to charge transfer. The DFT-SAPT method decomposes the
overall non-covalent binding energy into Eele, Edisp, Eind, and Eexch, Eexch–disp,
Eexch–ind and δ(HF), and this allows the polarization component of the over-
all binding energy to be determined via the equation Epol(DFT-SAPT) = Eind +
Eexch-ind + δ(HF). Using the RVS and DFT-SAPT energy decomposition meth-
ods, Sastry and coworkers showed the major contributors to the cation–π
binding energy of benzene, phenol, and various heteroaromatics were the
Eele and Epol terms.69 It is worth noting that neither the energy decomposition
work by Lewis and coworkers, nor the work by Sastry and coworkers, directly
addresses the issue of whether cation–arene interactions are dictated by the
cation interacting with the π-electron density, the substituent, or both. Cat-
ion–substituent and cation–π interactions can both be explained as owing
their attraction to electrostatics and/or electron density polarization.
The medium in which cation–arene interactions are studied can have a
significant effect on the strength of the interaction, and this has been widely
disseminated experimentally.27,70 Using the SM5.42R/HF/6-31+G* level of
theory, Dougherty and Gallivan computationally showed that increasing
solvent polarity led to a decrease in the cation–π Ebind value.71 However, the
decrease was found to be minimal compared to the calculated decrease in
binding energy for salt bridges across solvents with different polarities. Sher-
rill and coworkers reported similar findings for cation–π interactions of ben-
zene where the cation is Li+, Na+, K+, or NH4+ using the polarizable continuum
model (PCM) computational approach; increasing solvent polarity decreases
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Modern Computational Approaches to Understanding Interactions of Aromatics 13

72
the strength of the cation–π interaction. Recently, Bania and coworkers
showed that the same solvent polarity trends hold for substituted aromat-
ics partaking in cation–π interactions with Li+, Na+, or K+ using the PCM
approach to model the solvents.73 The issue of specific solvation of water
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molecules was computationally addressed by Sastry and coworkers and they

reported that solvation of the cation in cation–π complexes decreases the
overall Ebind, while solvation of the aromatic enhances the binding strength.74
While most studies of cation–π complexes of substituted aromatics have
focused on the half-sandwich motif (Figure 1.1(b)), it is estimated that sand-
wich complexes (Figure 1.10), with alkali or alkaline earth metal cations,
are at least as abundant in biology.1 For instance, many of the studies that
describe the importance of cation–π binding in protein folding, structure and
function are in fact sandwich complexes.75,76 Modern computational work
has aimed to address the issue of the additivity of the Ebind values for the cat-
ion–π sandwich complexes (Ebind,S). The issue involves whether Ebind,S is addi-
tive, and is equal to the sum of the binding energies of the two corresponding
half-sandwich complexes (Ebind,HS), or whether Ebind,S is non-additive, and
Ebind,S < 2 × Ebind,HS. Initial work on this issue by Jiang and coworkers sug-
gested Ebind,S was additive and Ebind,S = 2 × Ebind,HS.77 More recent calculations
by Orabi and Lamoureux on the topic showed the binding energy of cation–π
sandwich complexes was non-additive, and Ebind,S < 2 × Ebind,HS.78 Subsequent
computational efforts by the Lewis group showed that a triple-ζ basis set was
required to observe the non-additivity of cation–π sandwich complexes.79
The Lewis group also showed that non-additivity was increased when less
polarizable ions were included in the sandwich complex (for instance, when
Li+ is the ion rather than Na+ or K+).79

1.3.2 Predicting the Strength of Cation–Arene Interactions

Early work on predicting the binding strength of cation–π complexes of sub-
stituted aromatics focused on the electrostatic potential and Hammett sub-
stituent constants.59 Dougherty and coworkers showed a correlation between
the calculated electrostatic potential of 11 aromatics and the Na+ binding
energy.34 These 11 aromatics included benzene, naphthalene, pyridine, and
eight substituted benzenes. This early work by Dougherty and coworkers

Figure 1.10 
General structure of cation–π sandwich complexes for two substituted
benzenes, where Y is any monovalent cation, X is any substituent, and
n = 1–6.
 View Online

14 Chapter 1
+
also suggested a correlation between the calculated Na -substituted benzene
cation–π binding energies and the Hammett substituent constant σm.34 Subse-
quent work by Jiang and coworkers investigated the cation–π binding of Li+,
Na+, K+, Be2+, Mg2+, and Ca2+ with aniline, toluene, phenol, benzene, fluoro-
Published on 15 November 2016 on http://pubs.rsc.org | doi:10.1039/9781782626626-00001

benzene, 1,4-difluorobenzene, and 1,3,5-trifluorobenzene, and an excellent

correlation was reported between the binding enthalpies and σTotal, which the
authors define as σTotal = (Σσm + Σσp).80 This is the only example of using the
σTotal parameter to predict the relative cation–π binding of substituted ben-
zenes, and Jiang and coworkers suggest it means both resonance and induc-
tion are important in cation–π binding.80 More recently, Suresh and Sayyed
showed that cation–π interaction energies correlated very well with the term
ΔVmin, which is the difference between the calculated molecular electrostatic
potential on the aromatic π-region for a substituted arene and the corre-
sponding unsubstituted analog.81 Suresh and Sayyed investigated multiple
aromatic frameworks, cations, and substituents, and they found that the
calculated ΔVmin performed very well in predicting the relative cation–arene
binding energy.
Recent work by Quinonero—in response to the Houk and Wheeler work—
suggesting that cation–arene interactions of substituted benzenes may be
dictated by both cation–π interactions and cation–substituent interactions
showed that a two-parameter equation involving a linear combination of the
electrostatic energy and the polarization energy correlated very well with the
cation–π binding energies of substituted aromatics.67 As noted above, for the
Quinonero and coworkers’ study, the energy due to electrostatics was approx-
imated using the calculated aromatic quadrupole moment, and the energy
due to polarization was approximated via the calculated aromatic dipole
polarizabilities. Another recent study noted above, by Lewis and coworkers
investigating the energy decomposition energies of cation–π interactions of
aromatics, showed a poor correlation between the binding energies/enthal-
pies and the Σ(σm + σp), Σσp, Σσm, and Θzz values for a large number of substi-
tuted benzenes.68 As a result, the researchers developed a cation–π binding
constant, Π+, from the cation-binding enthalpies of the mono-substituted
aromatics. Specifically, the substituent constant was derived from the equa-
tion Π+ = −log[(ΔH298(Na+–C6H5X))/(ΔH298(Na+–C6H6))], and the correlation
with the cation–π binding energies of the larger group of substituted aromat-
ics, mono-substituted and multi-substituted, was excellent.

1.4 Summary
Initial computational work on arene–arene and cation–arene non-covalent
interactions focused on the aromatic quadrupole moments. Over time, Ham-
mett substituent constants and aromatic electrostatic potentials were com-
monly employed to understand and describe arene–arene and cation–arene
interactions. Modern computational efforts have focused on the importance
of substituent–substituent interactions in the binding of arene–arene com-
plexes, and cation–substituent interactions in the binding of cation–arene
 View Online

Modern Computational Approaches to Understanding Interactions of Aromatics 15

complexes. In addition, energy decomposition methods, such as SAPT, are
becoming more widely employed to better understand the non-covalent
interactions of aromatics. Future work will surely see energy decomposition
methods applied to larger aromatic systems. Furthermore, the importance of
Published on 15 November 2016 on http://pubs.rsc.org | doi:10.1039/9781782626626-00001

π–π versus substituent–substituent interactions in understanding the nature

of the attraction in arene–arene complexes, and the importance of cation–π
versus cation–substituent interactions in understanding the nature of the
attraction in cation–arene complexes, will certainly be investigated with
larger, polyaromatic, systems. The concluding chapter of this book describes
new directions in organic materials chemistry that are spawning this interest
in larger, polyaromatic systems.

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Exploring the Variety of Random
Documents with Different Content
 PAYNTER FAMILY. 15 Nicholas Painter of Anne Arundel! co.,
in the Province of Maryland, Gent., now residing in London. Will
dated 8 Sep. 1684; proved 8 Oct. 1G85 by Henry Bray. (423 Cann.)
To my cozen Hen. Bray of London, glazier, 4000 acres in Dorchester
co., Maryland. To my bro. Roger Painter of Andover, co. Hants,
husbandman, 700 acres at Wye River in Talbott co. To my sist. Kath.
Painter of Andover, sp'', 700 acres in Anne Arundell co. To M"
Barbara Trinder of Abchurch Lane, sp^ 1050 acres in Caecill co. To
Kath. Keate, dau. to Jn" Keate of Andover, 400 acres in Tuckahoe in
Talbott co. To W'" Hawkins of London, sc^ i of 1000 acres in Ctiester
River in Talbott co., & of 1700 acres in Dorch"' co., & of 900 a. in
Cfficill co., all which were granted to me by patent. To Jn" Hawkins
of Lond., distiller, £5. My negros Tom & Sarah to be free. All res. to
Heu. Bray, he sole Ex'or. Witnessed by William Evans, Joseph
Huckebutt, John Jenkins. John Paynter. Will dated 7 June 17—. To
my wife Ann .... of estate in lieu of dower. To my son John all my
estate subject to charges .... To my son W"" .... Benjamin Paynter
£800 c. at respective ages of 21, & £60 yearly till then. To my dau.
Ann .... To my dau. Hester the like sum of £800 c Catherine £800 c.
To ... . the like sum. Mary .... my wife now enseint .... If my son
John die without issue then to my son W"', and in default to my son
Joseph, then to my son Benj°. My brother W™ to have 6 years for
payment of his debt. Col. Edw'' Byam, Major John Tomlinson, M''
Francis Carlile, Cap' John Duer, & my wife Ex'ors. Before Walter
Douglas, Esq., was sworn M'' Rich'' Sherwood 5 Jan. 1712-13. Sam',
son of my brother Sam' Martin, £100 c. All my plantation to my
godson W™, 2" son of my brother-in-law Col. John Gunthorpe, if he
die without issue then to his brother George, the 3'"* son. Witnessed
by Rowland Ash, jun., Nicholas Collins. Before Edward Byam, Esq.,
was sworn Capt. Rowland Ash 10 June 1736. Recorded 7 Sep. 1736.
Mary Paynter of Antigua, spinster. Will dated 1 Sep. 1769. £50 c. for
my funeral. To my sister Cath. White my negro. My negro woman to
Billy Elliot, son of Sam' Elliot, Esq., and in default of issue to his
brother Sam' Elliot, then to his sister Nancy Elliot. To my said sister
my clothing & £100 c, & to her daus. £100 between the 3. To my
cousin Ann Byaui, widow of W"" Byam, £50 c, & £50 c. each to my
cousin M'" Harry Byam, M'* Alice Eliot, wife of Sam' Eliot, Esq., & to
M''^ Anne, wife of Anthony Wyke, Esq., & £50 amongst Harry
Byam's 3 daus. Polly, Nancy, & Hetty Byam. All residue to Billy Eliot.
My cousin Ann Byam Ex'trix. Witnessed by Ashton Warner Byam.
Before Hon. Thomas Jarvis, President of H.M.'s Council, was sworn
Ann Warner of Antigua, widow, who stated that Ashton Warner
Byam, Esq., late of Antigua, now of St. Vincent, had been absent for
eight or niue years, 10 April 1781. Recorded 28 May 1781. William
Painter of Belfast Division, Antigua. Will dated 9 March 1721-2. To
my wife Cath. my black horse & saddle of £20 & a negro. To my dau.
Eliz"" £400 c. To my grandson John Burton £50 c. at 21 in lieu of a
negro I promised my dau. his mother Eliz"'. To my dau. Cath. £400
c. at 21. To my dau. Mary the same at 21. To my son John the same
at 21. To my son Sam' the same at 21. To Peter Delany for the care
his mother took of me £25 c. at 21. All my estate to my son W", & in
default to my son John, then to my son Sam', then to my daus.
eijually. My wife, John Gunthorpe, W"' Painter, John Brunckhurst, &
John Richards Ex'ors. Witnessed by Walter Sydserfe, Nathaniel
Crump, Henry Browne. Before Edward Byam, Lieut.-Governor, was
sworn Nathaniel Crump 27 Aug. 1724. Recorded 8 Dec. 1747.
William Paynter, Esq. AVill dated 11 June 1735. Col. John Gunthorpe
& Col. John Tomlinson to be Ex'ors, & to pay £500 out of the profits
of my estate to each of my unmarried sisters Eliz"" & Mary Paynter
above what is bequeathed them by my late brother's will. To my
godson Margaret Paynter of Antigua, widow. Will dated 11 Sep.
1777. To Mary Monteigue 6 silver spoons & my sugar tongs. To my
sister-in-law Mary Pigott my clothes. To Jas. Watson Roberts, son of
Rob' Roberts, 3 negros. To Rob' Roberts, jun., son of Rob' Roberts, a
negro. To my niece Eliz'" Roberts, wife of Rob' Roberts, my silver
tankard & all furniture. Rob' Roberts Ex'or. Witnessed by Benjamin
Roberts, Mary Wilson. By Thomas Shirley, Esq., was sworn Mary
Wilson 3 June 1783. Recorded 12 June 1783. 1671. 'Sir Tobias
Bridge's Barbadoes Regiment. Captain-Lieut. John Painter went in
that capacity, continued with the regiment, and stays in Barbadoes.
(Colonial Calendar, ' America and West Indies,' p. 258.) 1676.
Captain Samuel Painter, 75 acres. Surveyed 1676. 1678, July 20.
Samuel Jones, Esq., leases 150 acres for 99 years to Edmond Painter
and George Digby. 1679. Edmond Painter granted 4 acres on 7 Aug.
1677 by Colonel Philip Warner. Surveyed 12 Marcli 1679. 1679, Dec.
26. Samuel Jones sells to Edmond Paynter 75 acres at New North
Sound. 1681. Edmond Painter granted a patent for 123^ acres 23
July by 'Sir W. Stapleton. 16 Feb., 8 Queen Anne. John Paynter of
Antigua, Gent., and Ann his wife for £1500 currency sell to John
Richards of Antigua, Gent., 85 acres in Nonsuch. Captain William
Paynter of Belfast Division i: 9 March 1721-2 ; sworn 27 Aug. 1724.
07 ; bur. 13 March 1721 at St. Philip's. Will dated=rCatherine ....
Hving 1721. Elizabeth Gather Paynter, Hester Paynter. Payn- Mary
Paynter, bur. ter, mar. 6 May •22 Sep. 1779, spin1729, at St. ster, at
St. George's. John's, William Will dated 1 Sep. White ; living 1769 ;
sworn 10 1769. April 1781. J...I William Paynter. Samuel Paynter,
Catherine Payn- Mary Payn— living 1721. ter, mar. 3 Feb. ter, mar. 18
John Paynter, a — minor 1721. Elizabt. h Payn ter, mar Hall. Thomas
PiBurton, gott. 1732, at St. Junel735,at John's, John St. George's,
Hall.
 16 THE HISTORY OF ANTIGUA. 1715, April 6. William Lyell
of Antigua, tailor, leases to Mrs. Anne Paynter, widow and relict of
Captain John Paynter, 4 acres. (Her son Mr. John Paynter.) 1716,
Aug. 1. William Painter petitions for 10 acres, lately belonging to
John Hall, deceased, now descended to Samuel Hall who resides in
Jamaica. 1726, Nov. 12. In Chancery. Heir of William Paynter,
deceased, v. Ex'ors of John Paynter. Paynters in St. George's Parish
in 1852 contained 272 acres, and was owned by K. B. Osborn, M.D.
In 1789 it consisted of 278 acres and 148 slaves. (See Gunthorpe
Deed for its boundaries.) About the year 1790 Mr. Samuel Painter, a
free colored man of Antigua, and a member of the Methodist
Society, came to reside in Grenada and to labour as a mechanic. (Dr.
Coke's ' History of the West Indies,' vol. ii., pp. 68 and 86.) Parish
Kegister of St. John. Baptized. 1710 July 27 Joseph & Benjamin
children of Cap' John Painter & his wife. 1735 [blank'] S. of John
Paynter & his wife. 1738 Oct. 31 John y« S. of John Paynter & his
wife. 1758 Feb. 28 William the S. of Edward Paynter & Elizabeth his
wife. 1759 Nov. 12 William the S. of Edward Paynter & Elizabeth his
wife. Married. 1729 May 6 William White and Catherine Paynter.
1732 Feb. 3 John Hall and Catherine Paynter. L. 1741 Jan. 6 John
Painter and Mary Crawford. 1753 Nov. 11 Edward Paynter and
Elizabeth Lony. L. Buried. 1718 June 8 William Paynter. 1745 Mar. 31
Jarvis Painter. 1748 Nov. 22 Mary Paynter wife of .John I'^inter. 1748
Feb. 27 John Painter. 1752 Nov. 22 .... Paynter. 1756 May 16
Piebeccah Paynter. 1764 April 4 Samuel Paynter, P. 1768 Dec. 30
Elizabeth Paynter. Parish Register of St. George. Baptized. 1735 S. of
John Paynter & his wife. 1738 Oct. 31 John y«^ S. of John Paynter &
his wife. Married. 1734 Aug. 8 John Paynter, Esq"', & Elizabeth
Piggott, Spinster. 1735 June 18 Thomas Pigott & Mary Paynter,
Spinster. Buried. 1734 Oct. 13 Sarah y« wife of Coll" William Paynter.
1740 Jan. 6 Elizabeth Paynter. 1779 Sep. 22 Miss Mary Paynter.
Parish Register of St. Peter. Buried. 1772 Mar. 22 Edward Painter.
Parish Register of St. Philip. Buried. 1711 Jan. 13 Edmond Paynter.
1717 April 13 Ann Paynter. 1721 Mar. 13 Cap' Will"' Paynter. St.
George's Churchyard. On a head stone : — Sacred to the Memory of
Samuel Paynter Who departed this life On W" of April l^U Ayed 79
years. In Ringwood Churchyard, co. Hants, there is a flat stone with
an inscription to the memory of William Paynter who died 1711, and
to a dau. of William and Joan Paynter who died 15 Jan. 1753, set.
53, and on a shield these arms : .... within a hordure .... three billets
.... (Paynter). Crest : 7'hree pheons handled .... two in saltire, one in
pale. These are approximately the bearings of the Cornish family
whose pedigree was entered in the Visitation of that county.
^^ftitcjwt oi ^earne. PEARNE^p. I Heni-y Pearne of
Antigua,=pGrace, dau. of Colonel Captain William Pearne=rMary,
only child of Captain=j=(? Henrietta ^^sq.. Member of Council ;
Philip Warner, Deputy of Antigua; bur. 15 Colonel of Militia; bur.
Governor of Antigua ; April 1726 at St. John's. 21 Jan. 1705 at St.
John's, mar. 21 March 1689 Will dated 12 April Will dated 17 Jan.,
and at St. Paul's; living 1726. Bworn 23 Jan. 1705-6. 1714. John
Slicer, and John relict of Robert Pearne. Freeman ; mar. circa 1706. .
bur. 23 April 1730 at St. John's.) Robert Pearne, only= son and heir,
a minor in 1705 ; owned "Blubber Valley "of 1200 acres and "
Musketo Cove " of 600. Will dated 12 July 1717 ; proved 11 Nov.
1718. (221 Tenison.) ■Mary, youngest dau. of William Lisle, Esq., of
Evenley, co. Northants;died 13 May 1756. M.I. lat Evenley. Will dated
9 June 1750; proved 13 July 1756. (201 Glazier.) I I Jane Pearne,
under 18 in 1705 ; living 1714. Elizabeth Pearne, under 18 in 1705 ;
mar. Captain Toby Lisle. R.N., son of Wiir im Lisle of Evi/ ley, Esq.
Will datt.d25 Jan. 1717; prored P.C.C. 21 July 1719. John Henry
Pearne, living 1726; dead 1749. Richard Hamilton Pearne, livMary
Ann Pearne, mar. 1731, at St. ing 1726 and Paul's, Bar1749. William
Loolin Pearne, ? bur. 8 Jan. 1730 at St. John's; dead 1749. ton ;
living 1749 a widow. Sarah Grace Pearne, living 1726 ; dead 1749. I
Henrietta Pearne, living 1726. Robert Pearne, only son and heir, bur.
31 March 1757 at Evenley. Will dated 26 Jan. and proved 4 April
1757. (132 Herring.) Mary Pearne, only dau., under 17 in 1717 ; mar.
Samuel Pateshall of St. George's, Hanover Square, Esq. ; both living
1757.
 PEARNE FAMILY. 17 Henry Pearne of Antigua, Esq. "Will
dated 17 Jan. 1705. To my wife Grace my plate, furniture, coach &
horses, 3 negros, & ^ of all produce. To my 2 daus. Jane & Eliz'"
Pearne £2000 st. each at 18, & £50 a year till then. To my brother
W™ Pearne £.300 c, my clothing & fiisil. To my brother Cap' John
Pearne all the rents of my plantation in S' Christopher's, now in the
possession of Michael Lambert, Esq., till my son Robert be 21. To my
sisters-in-law M" Ann Barnes & M"'" Mary Burgeois & my cozen Eliz""
Burgeois £20 c. each. To my friend W™ Nevine, Esq., my bay mare.
To John Mabson £10 c. All residue to my son Rob' his heirs, & in
default to any younger son, then to my daus. equally, then to my
said 2 brothers John & W'". ]\Iy son Rob' Ex'or, & during his Minority
Col. EdW^ Byam of Antigua, Esq., Archibald Hutchinson of the Inner
Temple, Esq., Barry Tankard of Antigua, Esq., Capt. John Perry late
of Antigua, Daniel Mackinen of Antigua, Chirurgeon, & my wife
Ex'ors in Trust. Witnessed by Gousse Bonnin, Dorothy Crafford,
Margaret Fowler. By John Yeamans, Esq., were sworn Gousse
Bonnin, Chirurgeon, and Margaret Fowler, spinster, 23 Jan. 1705-6.
Recorded 25 Jan. 1705-6. Robert Pearne, Esq., of Antigua. Will dated
12 July 1717; proved 11 Nov. 1718 by Patrick Lisle, power reserved
to the other Ex'ors. (221 Tenison.) To my wife Mary £3000 charged
on my estate in Blubber Valley. To my dau. Mary Pearne £1000 at 17
(in case my wife is now enceint with a boy) & £40 yearly till then. If
the child be a girl then the £1000 to be void, & to my 2 daus. all my
estates & negros at 17. My wife to be Guardian. In case of failure of
issue to my daus. my estate to go to such persons as are named in
the will of my late father Henry Pearne, Esq. My worthy friends &
relations Col. EdW^ Warner, Capt. Patrick Lisle & Cap' Toby Lisle,
Ashton Warner, Esq., & W™ Pearne, Esq., Ex'ors, & £50 apiece. All
residue of my personal estate to my dau. Mary & to the child to be
born if a girl, but if a boy then all my estate to hiui. Witnessed by W.
Hill, Muriel Mackenzie, Michael Arnald. William Pearne, Gent. Will
dated 12 April 1726. To my niece Henrietta, dau. of my late brother
John Pearne, Esq., £100 c. to be paid out of the legacy left me by
my brother Henry Pearne. All residue to my Ex'ors in trust to sell &
invest proceeds & divide the same equally among my children John
Henry Pearne, Rich"! Hamilton Pearne, W"^ Loolin Pearne, Mary Ann
Pearne, & Sarah Grace Pearne. Hon. Archibald Cochran, Esq., Chas.
Dunbar, Henry Osborn, Ashton Warner, Esq., Ex'ors & Guardians.
Witnessed by Roger Adams, W. Alexander, Edward Rickett. Before
William Mathew, Esq., was sworn William Alexander. Francis Pearn,
shopkeeper. Will dated 9 Sep. 1729. All my estate to my wife Mary.
To M'' Thos. Kerby, M' Jacob Thibou, M'' Thos. Stevens Ex'ors with
my wife, all my estate after my wife's death or marriage in trust for
my children equally. Witnessed by Rachel Hughes, Robert Smith,
George Jennings. Before Edward Byam, Esq., was sworn Robert
Smith 26 Nov. 1729. Mary Pearne. Will dated 9 June 1750. On 13
July 1756 adm'on to Robert Pearne the son. (201 Glazier.) £20 to my
sister for mourning. My Mother orders £20 a year to be paid to my
aunt Bridget Lisle, & after my aunt's death £4 a year to Anne South,
wife of John South of Mixbury, & all residue between testatrix's son
& dau. equally. Deed of gift new signed 26 Nov. 1753 & 26 March
1756. On 15 July 1756 were sworn Mary Pateshall, wife of Samuel
Pateshall of St. George's, Hanover Square, only dau. of Mary Pearne
late of Evenly, co. Northampton, and Bridget Vipont of Hampstead,
widow, Robert Pearne and Mary Pateshall, the son and dau., being
the only children of deceased. Robert Pearne of Isleworth, Esq. Will
dated 26 Jan. 1757; proved 4 April 1757 by the Right Hon. Sir John
Willes, John Willes, and Charles Spooner, Esquires. (132 Herring.)
The use of my plate, etc., as per schedule to my sister Mary
Pateshall for life, then to her dau. Mary Pateshall to whom I give
£1000 at 23. To John Willes, Esq., 1" son of the R' Hon. Sir John
Willes, K', 1^' Lord Commissioner of the Great Seal & Lord Chief
Justice of the Court of Common Pleas, my chariot & harness, my
diamond shirt buckle, & my picture. To Edw'' Willes, Esq., 2'' son of
Sir John, my gold-headed cane & 20 gs. To Chas. Spooner, Esq.,
youngest son of John Spooner of Bloomsbnry, Esq., my diamond ring
with 2 large & 2 small brilliants. To the Hon. M''^ Marg' Tufton & the
Hon. M" Mary Tufton, aunts to the present Earl of Thanet, the
pictures of my mother & my grandfather W" Lisle, my silver tumbler
& agate snuff box. To my servant Jas. Gulliver my clothing, the use
of my silver watch for life, then to Jas. Byers, shopkeeper, of
Brackley, co. Northants, also £10 a year. To my old coachman Thos.
Tarman of Evenley £6 a year. To Jas. Gulliver my tenement in co.
Northants with the use of the furniture & implements there for life,
then to John Willes, Esq. £40 a year to M" Hannah Axford formerly
Lightfoot, niece to the late M"' John Jefferyes, watchmaker in
Holborn. The £4 a year given by my late mother Mary Pearne by will
to M''^ Ann South of Mixbury, co. Bucks, to be continued. My Ex'ors
to give to my cousin Eliz. Bowles, wife of the Rev. D'' Tho. Bowles,
Rector of Brackley, the pedigi-ee of my family. To Sam^ Pateshall,
husband of my sister Mary, 5 gs. To each servant 10 gs. To the poor
of Brackley & Evenley 10 gs. All residue of plate & household goods
in my house at Isleworth to John Willes, Esq. All residue of personal
estate to Sir John Willes & John Willes, Esq. (legacies to be charged
on my plantation in Antigua), in Trust to pay £300 a year to my
sister Mary Pateshall. ^ of my plantation in Antigua to Sir John
Willes for life, then to his 1'' son John Willes, then to Tho. Abney of
Willesby, co. Derby, Esq., & to Nath' Worley in Trust for the 2'^ son
of John Willes, & in default to Chas. Willes, youngest son of Sir John.
The other ^ to Chas. Spooner & his heirs, then to Chas. Willes Sir
John Willes, John Willes, Esq., & Cha. Spooner, Esq., Ex'ors.
Schedule of plate follows. M''* Collier's f icture. Close Roll, 14 Geo.
II., Part 9, Nos. 4 and 5. In^aenture naie 18 Dec. 1740 between
Robert Pearne of t\he parish ci E-ienly, Northants, Esq. (sou and heir
of Robe'rt Pearue, late of Antigua, Esq., deceased, grandson and heir
male of Henr^ Pearne of Antigua, Esq., deceased), of the one part,
and Drury Otley the younger and Charles Lavall Molineux of St. Kitts,
Esquires, of the other part, witnessf th that Robert Pearne, in
consideration of 5s., sells to Drury Otley and Charles Lavall Molineux
all that plantation in the parish of St. Mary Cayon in St. Kitts,
containing 120 acres, formerly the plantation of Robert Skerrit,
deceased, and afterwards by letters patent under the Great Seal of
H.M.'s Charibee Islands duly recorded, etc., and in a special verdict
found by the jury on the tryal of an action of ejectment brought
against William Otley and Elizabeth Otley his wife, and Margaret
Willet the younger, on the demand of Robert Pearne in the Court of
King's Bench and Common Pleas, held at the town of Basseterre,
granted by King William III. unto Henry
 18 THE HISTORY OF ANTIGUA. Pearne therein mentioned,
and to his heirs for evermore, and now in the tenure of Patrick
Blake, Esq., and late in that of Martin Blake, Esq., and heretofore in
that of Ralph Willet, Esq., and bounded ac the foot with the common
path, to the E. with the lands heretofore of Charles Nephew Francis
Hicky and now of [blank'], S. with the lands heretofore of Lewis and
now of [blank'], and W. with the lands of Clement Crook, Esq., and
so to its extent to the mountains, and all other messuages and
plantations, etc., whatsoever of Robert Pearne or of any person in
trust for him in the said parish, and all messuages, pastures,
feedings, mountain land, timber, trees, woods, underwoods, with the
ground and soil of the same, waters, watercourses, etc., to have and
to hold to Drury Otley and Charles liavall Molineux for one whole
year at the rent of a peppercorn, if demanded, to the intent and
purpose only that they, by virtue of these presents and of the statute
of transferring uses, may be in actual possession, and enabled to
accept and take a grant and release of the reversion and inheritance
to them and their heirs for ever. J. Spooner. John Sharpe, No. -1.
Indenture made 10th Dec. 1740 between Robert Pearne of the
parish of Evenly, Northants, Esq. (son and heir, etc.), of the 1st part,
William Otley and Elizabeth Otley his wife and Margaret AVillet the
younger of St. Kitts, singlewoman (which said Elizabeth and
Margaret are the daughters and coheirs of John Willet, and cousins
and coheirs of Ralph Willet, late of St. Kitts, Esq., deceased), of the
2nd part, and William Coleman of London, merchant, of the 3rd part,
and Drury Otley the younger and Charles Lavall Molineux of St. Kitts,
Esquires, of the 4th part. Whereas in the year 173G an action of
ejectment was brought against William and Elizabeth Otley and
Margaret Willet on the demand of Robert Pearne in the Court of
King's Bench and Common Pleas, etc., for the recovery from them of
the possession of a messuage, 200 acres of kiid, 200 acres of cane
land, and 100 acres of pasture, and 100 acres of wood in the parish
of St. Mary Cayon, and the said William and Elizabeth Otley and
Margaret Willet having appeared and pleaded the general issue of
not guilty, the action came on to be tryed the second Thursday in
June 1736 when the jury returned a special verdict, and afterwards
upon the 15th June 1736 upon arguing the said verdict the Court
gave judgment that Robert Pearne the lessee should recover against
the others his term in the said 200 acres, etc., but Robert Pearne
having released to them his action as to the messuage, and also
remitted to them all damages, costs, etc., by him sustained, and also
all judgments and executions thereon had, they were acquitted by
the Court as to the messuage ; and whereas William and Elizabeth
Otley and Margaret Willet afterwards brought a writt of error from
the judgment before the Governor and Cour.ii', anu! assigned the
general error, and Robert Pearne havii.g filed a joinder in error, the
writt of error on the 31st Aug. 1737 came on lo be argued before
the Governor and Cjuncil as a Cou'rt of Errors, when the former
judgment was affirmed with costs on the writt ; and whereas William
and Elizabetii Otlfjy and Margaret Willet prayed and were allowed an
appeal to the King's Most Excellent Majesty which is still depending ;
and whereas by articles of agreement of the 21st May last past
between Robert Pearne, late of St. Kitts, I ut then residing in
London, of the one part, and William Coleman (on behalf of the
others), of the other part, reciting as above, it was further recited
that in order to prevent any further litigation it was agreed that
Robert Pearne should release and confirm all his right, etc., to
William and Elizabeth Otley and Margaret Willet in consideration of
£1000 sterling, £100 to be paid on the ensealing, and £900 on the
5th Sep. next ensuing in case St. Kitts continues till then in the
possession of the Crown of Great Britain, and shall not be before
taken by the Spaniards or any other enemy to the Crown of Great
Britain, it was witnessed that William Coleman has paid Robert
Pearne £100, and on payment of the residue Robert Pearne agrees
to make proper conveyances. Now this Indenture witnesseth that
Robert Pearne has granted, etc., to Drury Otley the younger and
Charles Lavall Molineux the 120 acres, formerly the plantation of
Peter Skerrit, deceased, etc., as to one moiety to the only use of
Elizabeth Otley and her heirs, and the other moiety to the only use
of Margaret Willet and her heirs for ever, and William Coleman
transfers to Drury Otley and Charles Lavall Molineux and their Ex'ors
the said judgments, etc., to the sole benefit of William Otley and
Elizabeth his wife, and Margaret Willet. Close Roll, 17 Geo. II., Part
20, Nos. 21 and 22. Indenture made the 28th March 1743 between
Robert Pearne of Evenly, Northants, Esq. (son and heir of Robert
Pearne of Antigua, Esq., deceased, and grandson and heir of the
body of Henry Pearne of Antigua, Esq., deceased), of the one part,
and William Johnson of Sergeants' Inn, Chancery Lane, Gent., of the
other part, witnesseth that in consideration of 5s. Robert Pearne
grants, etc., to William Johnson Blubber Valley Plantation in the
parish of St. Mary and division of Bermudian Valley, Antigua,
containing 1200 acres, bounded E. with the lands of George
Jennings, Esq., deceased, Thomas Stephens, Esq., deceased, William
Allam, John Sedgwick, and Robert Christian, W. with the plantations
of the Hon. Valentine Morris, Esq., lately deceased, and the lands of
William Dunning and Sheers Stephens, N. with the plantation of the
Hon. Samuel Watkins, Esq., and of George Jennings, Esq., deceased,
and S. with the lands of Francis Franklyn, Robert Christian, and the
late John Forster, deceased, and the dwelling house, etc., and all
those negro and other slaves (names given), 45 men, 49 women, 15
boys, and 20 girls, and all those 50 horses and 100 head of cattle
thereon, and all that other plantation called Musketo Cove in the said
parish and division containing 600 acres, bounded E. with Perrie
York's Plantation, W. with the sea, N. partly with the lauds of George
Leonard and partly with the sea, and S. with the plantation of
Valentine Morris and the sea, and all that stock house, and also 20
horses and 100 head of cattle thereon, and also all that other parcel
of land called James Red's Hill containing 30 acres in the said parish,
bounded E. in part with the plantation of Valentine Morris and part
with the sea, and W., N., and S. with the sea, to have and to hold for
one whole yeai', yielding therefore one peppercorn, to the intent he
may be in actual possession, and thereby enabled to take a grant
and release of the reversion and inheritance. No. 21. Indenture
made the 29th March 1743 between Robert Pearne, etc., of the one
part, and William Johnson, of the other part, witnesseth that in
consideration of 10s. Robert Pearne grants, etc., to William Johnson
(as in No. 22), to the intent that all estates tail and remainders, etc.,
may be effectually barred and destroyed according to the laws of the
Leeward Islands, to the only proper use of William Johnson and his
heirs and assigns for ever. Hugh Hamersley, William Rowlandson,
witnesses. CloS(^ Roll, 19 Geo. II., Part 16, Nos. 1, 2, 8, and 4.
Indenture made the 14th March 1745 by which Robert Pearne
conveys to William Johnson Blubber Valley Plantation, etc., and all
the dwelling-house, etc., and also all and every those negro and
other slaves (as iu 17 Geo. II.), and also all Musketo Cove Plantation
containing 600 acres, and 20 horses and 100 head of cattle, and
also James Red's Hill
 PEARNE FAMILY. 19 containing 30 acres, and also all those
36 acres lately recovered by Eobert Pearne from the said Valentine
Morris, and now in the possession of Martin Blake, Esq., or his
assigns for one whole year, and Robert Pearne appoints Stephen
Blizard, Nathaniel Gilbert, and Martin Blake, all of Antigua, Esquires,
his Attorneys. John Martin, Tobias Lisle, Harry AVebb, witnesses. No.
3. Indenture made the 15th March 1745 between Robert Pearne, of
the one part, and William Johnson, of the other part, witnesseth that
in consideration of 10s. Robert Pearne conveys to William Johnson
(as in No. 4), to the only proper use of William Johnson and his
heirs. No. 2. Indenture made the 17th March 1745 between William
Johnson, of the one part, and Robert Pearne, of the other part. No.
1. Indenture made the 20th March 1745 between the above (simply
the reconveyance, with the same Attorneys and the same
witnesses). Close Roll, 29 Geo. II., Part 2, Nos. 1 and 2. Indenture
made the 3rd Dec. 1755 between Robert Pearne of Evenly, otherwise
Imley, Northants, Esq. (only son and heir of Robert Pearne,
heretofore of Antigua, Esq., deceased, who was only son and heir of
Henry Pearne, heretofore likewise of Antigua, Esq., deceased), of the
one part, and Robert Christian of Antigua, Esq., of the other part,
witnesseth that in consideration of 5s. Robert Pearne conveys to
Robert Christian all Shackerley's Plantation containing 300 acres, late
in the tenure of Charles Dunbar or his tenants, and heretofore in the
occupation of Francis Shackerley, .... Duncombe, or ... . Martin, and
formerly purchased by Henry Pearne the grandfather from John
Barnes and Ann Bai-nes of Antigua, for one whole year. Thurston
Blackman, William Marshall, witnesses. No. 1. Indenture made the
4th Dec. 1755 as above. Whereas Articles of Agreement were made
and concluded on the 20th May 1752 between the said Robert
Pearne (only son and heir-at-law of Robert Pearne, deceased), of the
one part, Robert Christian, of the other part, by which after reciting
that Robert Pearne claimed to be seised of certain lands in the parish
of St. Mary in Antigua called Shackerley's Plantation, containing 300
acres, mostly wood and coppice, then in the occupation of Charles
Dunbar, Esq., or his tenants, and heretofore (as in No. 2), and also
after reciting that Robert Christian had contracted and agreed for the
absolute purchase upon the conditions hereinafter mentioned, it was
witnessed that in consideration of £500 Robert Pearne did agree to
forthwith produce all deeds, etc., whereby it might appear he was
seised of a good estate in fee simple, and also that he would (so
that he was not compelled to travel above 20 miles from his usual
place of abode), at the costs and charges of Robert Christian,
convey to him the said plantation, free from incumbrances
whatsoever, and Robert Christian did covenant and agree that on the
execution of the said conveyance he would pay a further sum of
£500 in full satisfaction of the purchase money, and it was agreed
that if Robert Christian should not approve of the title Robert Pearne
should nevertheless retain the first-mentioned £500, which should
be forfeited, and also reciting that Robert Pearne was seised of
divers other plantations, etc., in Antigua, but no other lands than
those on the 7th March then last in the tenure of Charles Dunbar
should be taken as any part of the lands contracted for by Robert
Christian ; and whereas Charles Dunbar hath by his Attornies William
Dunbar and Thomas Warner, Esquires, by Indentures dated the 10th
and 11th July last, conveyed to Robert Pearne the said lands and
hereditaments called Shackerleys, to the only proper use of Robert
Pearne and his heirs and assigns. Now therefore this Indenture
witnesseth that for carrying the said Articles into execution, and in
consideration of the £500 already paid, and also in consideration of
£500 to be paid at or before the sealing of these presents, and to
bar and destroy all estates tail and remainders, and vest in Robert
Christian an absolute inheritance in fee simple, Robert Pearne grants
and confirms to Robert Christian in his actual possession being all
that plantation (as in No. 2), and Robert Pearne appoints, etc.,
Thomas Elmes, Francis Farley, Simon Farley, and John Jeflfreson of
Antigua, Esquires, or any three of them, his Attorneys. 1695. Henry
Pearne conveys 300 acres (part of Jolly Hill Plantation) to General
Codrington. 1696. Captain Henry Pearne, a member of the vestry of
St. Mary's Parish, was rated on 750 acres and 74 slaves. On 17nl,
Aug. 12, was read the Act to enable Hen. Pearne, Esq., to sell
Blubber Valley Plant", reciting that Henrietta Warner, late y"= Wid. of
Col. Philip Warner, dec"", owned the said plant" of 380 acres, &by
her deed of 1 Mar. 6 W™ conveyed it to Esaii Burgois & to W°>
Barnes, late of Antigua, Gent., for 1 year, in trust for her own use for
life, & then for Hen. Pearne, Gent., husb"! of Grace her dau., for his
life, then to Grace Pearne for her life, then to their only s. & h. Rob'
Pearne & his heirs, reserving power to charge the estate with
200,000 lbs. The Negros are all dead & Hen. Pearne has spent
£3000 on the estate. (Minutes of Council.) 1706, June V. Colonel
Henry Pearne's estate in St. Mary's Parish was rated on 665 acres
and 150 slaves. 1712. In the Court of King's Bench and Common
Pleas Mary Lingham sued the Guardians of Robert Pearne, re the
Blubber Valley and Musquito Cove Plantations of 1200 acres and 100
negro men, 20 women, 20 boys, and 20 girls. 1713. John Pearne,
late Lieut.-Governor of Montserrat, has gone to England. (B. T.
Leeward Islands, vol. 13.) 1714. March 1. Mrs. Jane Pearne of
Antigua for £100 c. sells to her mother Mrs. Grace Pearne 4 negros.
1716. Mr. Pern was allotted pew No. 3 in St. Mary's Church. 1719,
Aug. 12. William Pearne, Gent., has a plantation of 100 acres in
Nonsuch Division, St. Philip's Parish, N. with Robert Freeman, Robert
Hunt, deceased, and Thomas Ske'-'it'i,' ^ with Thomas Skerrett,
Daniel Maningham, and [Robert F''ee.Tian, S. with Robert Freeman
and John Lu(is, Esq., and N cholas Lynch, W. with Nicholas Lynch
and Robert Hunt, de-eased. Patent granted. Jiary, widow of Robert
Freeman who died 1705, married secondly Mr. Perne, possibly the
above-mentioned William Pearne. Robert Pearce { ? Pearne), Esq.,
owner of large estates in Antigua and St. Kitts, married 28 Jan. 1744
the dau. of Mr. Pycraft. brewer, with 20,000/. 174.1, Jan. 6. In
Chancery. Charles Dunbar, Esq., Ashton Warner, Esq., the surviving
Ex'ors of William Pearne, deceased ; Richard Hamilton Pearne, Gent.,
and Mary Ann Barton, widow, the surviving children and. legatees of
William Pearne, Complainants, v. Elizabeth Freeman, Executrix of
Arthur Freeman ; John Tomlinson, Esq., Joseph Buckshorne, George
Thomas, Esq., Alice Freeman, widow. Executors of Robert Freeman
the younger, deceased.
 20 THE HISTORY OF ANTIGUA. No. 356. Pi-ivate. An Act for
vesting divers Slaves, late of Robert Pearne, of Isleworth in the
County of Middlesex, in the Kingdom of Great Britain, Esq., now
deceased, in Trustees, to be sold ; and for laying out, the Monies
arising by such Sale, in the Purchase of other Slaves, to be settled
upon the Trustees, and to the Uses of the Will of the said Robert
Pearne. Dated Cth May 177-4. No. -laS. Private. An Act to vest in
Trustees for Sale certain Negro Slaves devised by the Will of Robert
Pearne, Esquire, discharged from the Uses and Trusts declared,
concerning the same in and by the said Will ; and for investing the
Money arising by such Sale in real or Government Securities in Great
Britain, upon the like Uses and Trusts. Dated 28"> March 1780. For
an account of the Pearne estate see the Lingham Papers. 1731
Parish Register of St. Paul. Blarried. Barton & Mary Ann Pearne ; by
L. Parish Register of St. John. Buried. 1705 Jan. 21 Coll" Henry
Pearne. 1726 April 15 Cap' William Pearne. 1730 April 23 M''=
Henrietta Pearne. 1 730 Jan. 8 M' W™ Pearne. 1731 June 12 M''"
Sarah Pearne. Evenley Church, co. Northants. Here lies Interred the
Body of M'^ MARY PEARNE Wife of ROBERT PEARNE Esq late of the
Island of ANTEGOE and youngest Daughter of WILLM LISLE Esq'late
of Evenly at whose feet she desired to be laid on the left side of
Sister FRANCES LISLE She Died May r 13"' 1756. ^ctitfjrtt of ^txx^.
Arms. — On a lend .... hetween two cofh'ses ermine tliree lions
passant. Perry of London ; granted 1700. PERRY=F Micajah Perry*
of Leadenhall Street, Virginia-=pAnn, dan. of Dr. Richard Owen ;
merchant ; aged 23 in 1663 ; Agent to Governor Hamilton in 1710 ;
died 1 and bur. 10 Oct. 1721, aged, at St. Botolph, Bishopsgate. Will
dated 22 Dec. 1720 ; proved 3 Oct. 1721. (185 Buckingham.)
marriage licence dated 20 Oct. 1663, then aet. 24 ; bur. 1 March
1701. aet. 66, in the chancel of St. Botolpli, Bishopsgate. I I
Elizabeth Perry, A dau. uxor .... Evans 1720. Lowe. Richard Perry of
Leaden-=pSarah .... hall Street, merchant. Will living 1725 dated 1 5
April and proved 4 May 1720. (118 Shaller.) and 1753. I Micajah
Perry, Esq.,M.P. Lon-=p. . . . dau. of don 1727—1741 ; Alderman of
Cock Aldgate 1728—1746 ; Sheriff of London, 1734, and Colonel of
the Orange linendraper ; Regiment of Trained Bands ; died 1738.
Lord Mayor 1 738 ; died -I'l Jan. 1753 at Epsom, co. Surrey. Adm'on
14 Aug. 1753. (See ' Notes and Queries ' for July 1895.) .M'^jtph
Lowe of Charles Town, Virginia,=T=Sarah Susanna Johanna Mary
.,.nd of O'orshalton, co. Surrey, merchant. .... Lowe, Lowe. Lowe,
Will dfite Y' Jan. 1702 ; proved 17 March living Hving 1702-3.-, t'h
Degg.) | 1720. 1720. \ s.p. Ehzabeth Perry, under 18 in 1720; mar.
1733 Salusbury Cade, Esq., son of Dr. Cade ; his will proved 1773.
(240 Stevens.) Philip Perry of Lor.don, merchant ; under 24 in 1720;
living 1753. Sarah Perry, 1st dau., born 31 Aug. 1702 ; mar. 1 Oct.
1719 William Heysham of East Greenwich, Esq., M.P. for town of
Lancaster. He was born 10 Dec. 1691, and died s.p. 14 April 1727,
set. 35. M.I. at St. Paul's Walden, co. Herts. Will dated 22 April 1725
; proved 28 June 1727. (142 Fiirrant.) She was living 1753. * Eichard
Perry, of Newhaven 1 ()40, had Mary, bapt. 4 Oct. of that year ; 11
July 1647 ; and Grace, 2 Sept. 1649. A Richard Perry, merchant, of
London, w 1629. (Savage's ' Gen. Diet, of New Eng-.,' p. 400.)
William Perry was a Member of Council for Virginia in or before 1635.
(Colonial Calendar.) Samuel, 8 .June 1645 ; .Tohu, lamed in the
Royal Charter of
 PERRY FAMILY. 21 Periy= John Perry of Antigua, merchant ;
Provost^ Marshal-General of the Leeward Islands 8 William III. ;
born and died at Youghall, CO. Cork. Will dated 24 Jan. 1708, then
of St. James, Westminster ; proved 4 April 1713. (89 Leeds.) John
Perry, bur. 16 Feb. 1700 at St. John's. I I Anne Perry, widow of . .
Osborne 170! SamuelPerry, dead 1708. Esq. dau. mar. Nisbitt, =Mary
living 1708. I Anne Perry,=pRichard Rigby of 1st dau. and ~" " " "
coheir ; mar. when a minor ; ffit. 21 died 1731. Misley Hall, co.
Essex, Esq., son of Edward Rigby; formerly a woollen - draper in
Paternoster Row, and factor to the South Sea Company ; died 1730.
Will dated K! Aug. and proved 19 Nov. 1730. (315 Auber.) I I
Dorothy Perry, bapt. 28 Dec. 1703 at St. John's ; a minor in 1722 ;
mar. George Barker of St. Paul, Covent Garden, merchant ; both
living 1745. Elizabeth Perry, died intestate under 17 before 1722. I I
Sarah Perry, bapt. 28 Dec. 1703 at St. John's. Mary Perry, a miuor in
1722 ; mar. John Cleland of St. Peter Poor, London, and of South
Carolina ; marriage settlement dated 1 4 Nov. 1728 ; both living
1745. Edward Perry of Antigna,= Esq. ; Registrar 1704 ; bur. 20 Feb.
1716-17 at St. John's. Will dated 24 Feb. 1714 ; proved 23 May
1717. (101 Whitfield.) Edward Perry, bur. 12 Sep. 1691 at St. John's.
Samuel Perry, a minor in 1708. I I I Jonathan Perry, merchant, only
son, brother-inlaw of Hopefor Bendall 1727. (See vol. i., p. 40.) Mary
Perry, widow of ... . PuUen 1714. A dau., living 1708. Right Hon.
Richard Rigby, a Member of the English Privy Council ; Master of the
Rolls and Vice- Anne Martha Treasurer in Ireland ; M.P. Tavistock ;
Paymaster'in Ireland 1768—1782 ; died at Bath 8 April 1788, Rigby.
Rigby. bachelor, aged 65 or 06. Will dated 31 Dec. 1781 ; proved 19
May 1788 (see 'Gent. Mag.' for 1788, pp. 370 and 462). 1673. Henry
Perry of Antigua died intestate. Adm'on to Kath. Perry his relict 4
Aug. by Philip Warner, Esq. 1699. Henry Hartwell of Virginia, Esq.,
names M" Sarah Perry, wife of M'' lUch'^ Perry, £5. Micajah Perry &
Rich'' Perry of London, merchants & Ex'ors, £50. (134 Pett.)
Christopher Morgan of London. Will dated 22 March 1703-4. (45
Eedes.) Micajah Perry, Tho. Lane, & Richard Perry's bond dated 26
March 1700 for £2000, ditto & money £1000, debts in Virginia. My -
^ of tho ship " Perry & Lane," y^ of the ship " Hartwell," etc.
Micajah Lowe, late of Charles City, County and Colony of Virginia,
now of Casehanlton, co Surrey, merchant. Will dated 20 Jan., proved
17 March 1702 by Micajah Perry. (53 Degg.) To my uncle M' Micajah
Perry, my motherin-1. M'"* Eliz. Hamlin, my sisters Susanna Lowe &
Johanna Jarrett & Mary Lowe, rings. All residue to my wife Sarah,
she & my uncle Mic. Perry Ex'ors. Witnessed by Sarah Jos. Cooper,
Robert Dalley, Thomas Deubery. John Perry, late of Antigua, now of
St. James, Westminster, merchant. Will dated 24 June 1708; proved
4 April 1713 by Jonathan Perry the Guardian of Anne and Dorotiiy
Perry, minors, daus. of testator, who was last of Youghall, deceased;
proved 7 Oct. 1713 by Edward Perry ; power reserved to Anne and
Dorothy Perry ; proved 23 May 1717 by Jonathan Perry, Edward
Perry being dead ; proved 25 Aug. 1722 by Anne Rigby alias Perry,
now wife of Richard Rigby, and one of the surviving Ex'trices, she
being now 21 ; power reserved to Dorothy Perry. (89 Leeds.) To the
ministers & churchwardens of Youghall, CO. Cork, where I was born,
£300 c. to buy lands in the name of the bishop of the diocese, and
the profits to be distributed to the poor every 29* of May at the
church door. To the poor of Christ Church in the City of Cork £100 c.
in the same way. To the parish of S' John's, Antigua, £300 for the
purchase of annuity of £30 c. to be distributed in the same way. To
my sister-in-law Mary Perry, widow of my brother Sam' Perry, £30 a
year for life. To my sister Anne Osborne, widow, & to her daus. Mary
Mills & Joyce Osbourne £200 c. apiece, & to each of her
grandchildrer. £100 c. at 21, except John Freeman, son of Jas.
Freeman, to whom I have already given that sum. To my nephew
Sam' Perry £1000 c. at 21. To my well beloved wife Anne Perry £100
a year for life in lieu of dower, & all plate & furniture. To my dau.
Anne Perry £2000 which Major Long of Antigua owes me, & my
house & land adjoining Major Long's plantation in the town & parish
of S' John's, & £500, equal to a portion of £3000. To my dau.
Dorothy Perry all money due to me from Patrick Browne, late of
Antigua, deceased, & if less than £2500 to be made up to that sum.
To my dau. Eliz. Peny my moiety of a plantation in S' Mary's parish
with negros, etc., as lately rented by me to Patrick Browne,
deceased, which cost me £2290, also £210. To my dau. Mary all my
plantation in South Carolina & £500, equal to a portion of £25
 THE HISTORY OP ANTIGUA. Codkil. 24 Jan. 1716. To each
of my grandchildren £100 at 21. All plate with my coat of arms to my
son Jonathan. Edward Chester, j', my gold watch. Joseph Adams my
bed furniture. My sister Xisbitt my common prayer book & my late
brother John Perrie's seal. W Hopefor Bendall my sword, belt, & gun,
& to his dau. my goddau. the silver tankard I expect out of England.
M"' John Helden my gold-headed cane. Cath. Atkinson 40 pistoles &
a silver tankard. I have in my chest £747 belonging to M'' W" Moore
of Barbados. Witnessed by Peter Hasell, James Chester, George
.Jenkins. Kichard Perry. Will dated 15 April at London, proved 4 May
1720 by Sarah Periy the relict. (118 Shaller.) To my wife Sarah my
groundrent of Brewer's Key, now in the possession of the heirs of M"'
Rob. Richardson, dec'', at present £50 a year, & after her death to
my s. Micajah Perry, the mortgage of Little Stanbridge, co. Essex,
now let to M'' Joseph Tanner for £80 a year, with the manor &
quitrents of 35s. a year, the money I have lent the Crown on it being
much more than its worth, my rentcharge on lands in Sussex, now
paid by M'' Tho. Medley, Esq., of Lewis, £50 a year, my grouudrents
in Hatton Garden 18 years to come, £50 a year, & I pay Lord
Nottingham £6 a year, my groundrents in Moorfields £20 a year, also
plate, jewels, & furniture. To my son Micajah Perry the ^ of
Chester's Key, left him by M' Tho. Lane after the death of M''' Mary
Lane his widow, also my \. Whereas my father hath settled his
estate in Leadenhall-str. on me, after his death I give it my son
Philip, but my wife to have the house I live in rent free. I give her
also the leases of my 2 houses in Leadenhall-str., let to M' Motley
&:M'' Walker, till my son Philip be 24, at £38 & £30 less gl oundrent
of £13 6.?. M. My dau. Sarah Perry I have sufficiently provided for.
To my dau. Mary Perry £3000 bank stock. My dau. EHz. Perry £1000
bank stock, payable to both at 18. My stock in trade with my father
consists of a moiety, i of this to my son Micajah, \ to my son Philip at
24, & i to my wife. The monthly draughts for it to be not less than
£60 nor more than £90. I have sold my estate in Gravel Lane to
.John Blunt, Esq., subject to 2 annuities of £40. My wife sole Ex'trix.
Witnessed by John Ware, Charles Miller, James Johnston, John
Walkeley. Micajah Perry. AVill dated 22 Dec. 1720 at London ; proved
3 Oct. 1721 by Sarah Perry, widow, Micajah and Philip Perry. (185
Buckingham.) To Christ's Hospital £100. To the Work-house £100.
Mary & Susanna Lowe £50 each. My sister Eliz. Evans £20 a year. To
my 2 granddaus. Mary & Eliz. £1500 between them. Their' father's
will. I give them also my lease at Eaton, co Beds, which I hold of
Trinity Coll., Cam. To my grandson Micajah Perry my \ of Chester's
Key. To my 2 grandsons Micajah & Philip all residue & my moiety in
trade. To be buried in Bishop Church in the Middle Isle near the step
into the chancell where my dear wife lies. My dau. Sarah Perry & her
2 sons Micajah & Philip Perry Ex'ors. Witnessed 27 Sep. 1721 by
John Warr, James Johnston, John Walker. William Heysham of East
Greenwich, co. Kent, Esq. Will dated 22 April 1725 ; proved 28 June
1727 by Robert Thornton, and on 3 Feb. 1727 by John Marsh ;
power reserved to Robert Heysham. (142 Farrant.) My lands called
Greaves, near Lancaster, to my heirs male, remainder to M" Mary
Meller, then to the Corporation of Lancaster in Trust for 8 poor men.
To be buried in the church of S' Paul's Walden, co. Herts, near my
deceased uncle Rob' Heysham, Esq. £30 to the poor there. £300 to
my wife & £20 to her mother M'^ Sarah Perry, & to my wife's
brothers & sisters Micajah, Phillip, & Eliz. £10 each. 5Iy aunt W^
Hester Barker, & her dau. Eliz., & her son-in-law M"-Pall, & my cousin
Jane his wife £10 each. To my cousins Gyles & Rob' Thornton £10
each. My friend M'' John Marsh of Haberdashers' Hall £10. M'' Rob'
Antrobus of Eaton £10. To my wife plate, coach, & horses. All
freehold estate to the 1*' son of my body, & to each younger child
£2000. To my godson W-" Hall, son of M' Hall by Jane my cousin his
wife, £100. M'' John Green, surgeon in the Strand, £50. My cousin
Rob' Thornton £500. My friend John Marsh £1000. To Christ's
Hospital £200. All residue to any children, but in case I leave no
issue then to my cousin Rob' Heysham, then to my cousin Rob'
Thornton. They & John Marsh Ex'ors. Witnessed by Robert Haynes,
Thomas Roots, Charles Master. Richard Rigby of Mistley, co. Essex,
Esq. Will dated 18 Aug., proved 19 Nov. 1730 by Anne Rigby the
relict ; proved also 1 July 1742 by George Barker and Charles Gray,
the probate granted to Anne Rigby having expired by her death.
(315 Auber.) To my wife Anne ray mansion house Mistley Hall, &
confirm to her £150 a yr. by our marriage settlement, & I give her
also £250 a yr. & the use of plate & furniture, coach & 4 horses, 2
saddle horses, & £200. All my lands to my brother-in-law Geo.
Barker & Cha. Grey of Colchester, Esq., on Trust for my only s. Rich"!
Rigby in tail male, remainder to the heirs male of my dans. Anne &
Martha, my neph. Edw. Rigby, s. of my bro. Jas. Rigby. £1500 to ea.
of my s** 2 daus. My niece Mary Venn £20. To my friends Sir Chas.
Wager, K', & Sir John Eyles, Bart., & my brother Jas. Rigby, my
brothers-in-law John Stewart & Geo. Barker, my kinsman Jonathan
Perrie, & my good friends Edw. Pratter, Esq., of Jamaica, & the s"!
Chas. Grey, each a ring of 20 g"'. My s* s. to be G. of my daus. My
wife Ex'trix. Geo. Barker & Chas. Gray Ex'ors, & 50 g'^ each.
Witnessed by William Bumpstead, Thomas Barron, Rose Rye. Codicil
18 Aug. 1730. £1000 to my wife, payable out of the produce
received from the West Indies for improving Mistley Hall. £300 for
almshouses. 1753, Aug. 14. Micajah Perry, Esq., deceased. Limited
adm'on to Philip Perry of East Greenwich, Esq. It has been alledged
by Sarah Heysham, widow, & Gyles Thornton Heysham, Esq., that by
Indenture tripartite dated 11 April 1739 between Rob' Thornton of
East Greenwich, Esq., the surviving Ex'or of W" Heysham, of the 1^'
part, Micajah Perry, then Lord Mayor of Loudon, but late of Epsom,
Esq., deceased, & the said Philip Perry of London, merch', but since
of East Greenwich, Esq., of the 2'' part, & Gyles Thornton Heysham,
then of Stagnoe, co. Herts, Esq., of the 3'' part, that in consideration
of a marriage intended, & after solemnized, between W™ Heysham
& Sarah Perry, one of the daus. of Rich'' Perry, Esq. (now the said
Sarah Heysham, widow), £10,000 bank stock was assigned to Rob'
Heysham, Esq., Peter Godfrey, Esq., & Micajah Pei-ry for her
joynture, & if she died without issue for the use of her husband &
his heirs, & this sum became eventually vested in EdW" Tumour of
Bloomsbury Square, Esq., Micajah Perry, & Philip Perry. W™
Heysham died s.p. & appointed Rob' Thornton, Koh' Heysham, Esq.,
& John Marsh (both since dead) his Ex'ors. The £10,000 was ordered
by the Court of Chancery to be sold, & the reversion of it was
purchased by Gyles Thornton for £6100. Micajah Perry died intestate
within 12 months since. Adm'on to Philip Perry concerning the
£10,000 only. Limited adm'on of rest of goods passed Nov. 1757.
Another adm'on. Micajah Perry, formerly Lord Jlayor of London, but
of Epsom, Esq., deceased, widower, intestate, leaving Sarah Perry,
widow, his mother, since deceased, Philip Perry, Esq., his brother,
Sarah Heysham, & Eliz. Cade (wife of Salisbury Cade, Esq.) his
sisters.
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