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Aggregation of metallo-supramolecular architectures by

metallo-assembled hydrogen bonding sites†
Arnaud Lavalette, Floriana Tuna, Guy Clarkson, Nathaniel W. Alcock and Michael J. Hannon*
Centre for Supramolecular and Macromolecular Chemistry, Department of Chemistry, University of
Warwick, Gibbet Hill Road, Coventry, UK CV4 7AL. E-mail: [Link]@[Link]; Fax: 44 (0)24
7652 4112; Tel: 44 (0)24 7652 4107
Published on 08 October 2003. Downloaded by Institute of Chemistry, CAS on 6/30/2018 [Link] AM.

Received (in Cambridge, UK) 30th July 2003, Accepted 12th September 2003
First published as an Advance Article on the web 8th October 2003

Metal–ligand interactions are used not only to design alised with discrete sites that can form just a single hydrogen
metallo-supramolecular architectures but also to assemble bond. However, these sites are positioned such that in the
multiple hydrogen bond sites at the periphery of these metallo-supramolecular architecture they are brought together
architectures. The hydrogen bond sites aggregate the archi- to create a multiple hydrogen bond unit. Thus the metal–ligand
tectures into polymeric arrays with the selection of anion interactions will not only form the desired architecture but also
determining whether this is self H-bond aggregation or create the aggregation sites. This approach has considerable
anion-mediated H-bond aggregation. potential benefits in terms of simplifying the covalent synthe-
sis.
Biological systems make extensive use of non-covalent self-
assembly events to generate large and functional arrays.
Chemists too have made considerable progress in using
supramolecular interactions to design large molecules of
defined shape.1 Yet underpinning the supramolecular approach
is the use of covalent synthesis to design the building blocks.
Covalent synthesis introduces limitations to the size of building
blocks and thus of the subsequent supramolecular array. One
approach to circumvent this is to use multiple recognition
events in sequence, i.e. to use an initial supramolecular event to
construct small supramolecular units which are then used as The functionalised ligands (L1 and L2) are readily-prepared
building blocks in a second supramolecular event to give a from the condensation of the appropriate diamine with 6-hy-
higher order (and larger) aggregate. In this context we have droxymethylpyridine-2-carboxaldehyde which we have pre-
recently illustrated how metal–ligand and p–p interactions can pared in a single step from commercial 2,6-pyridinedimethanol.
be used in concert, p-interactions aggregating metallo-supra- Hydroxy groups were selected as they are simple units which
molecular units into larger nanoscale arrays.2 We have similarly can act as either H-bond donors or acceptors. We have
demonstrated sequential assembly using two different types of previously demonstrated that the unsubstituted analogues of
metal–ligand interaction.3 Very recently Bermejo, Gatteschi et these ligands react with tetrahedral monocations to form two
al. have applied the approach to design magnetic materials dinuclear species: a dimeric box (meso-isomer) and a dimeric
assembled from cupric helicates.4 Still more sophisticated helicate (rac-isomer).6 The introduction of ethyl groups onto
assemblies might be envisaged in which many different the spacer leads to the exclusive formation of the rac-isomer.
supramolecular events are designed into the assembly pathway. Reaction of L1 with [Cu(MeCN)4][PF6] in methanol led to
For this reason we are exploring routes to employ alternate the formation of a red-brown complex of dinuclear [Cu2(L1)2]2+
supramolecular interactions too. We describe herein the use of formulation. The room temperature 1H NMR spectrum in
hydrogen bonds to aggregate metallo-assembled boxes and CD3CN showed a single set of resonances, some of which were
helicates into larger arrays. broadened, and low temperature studies confirmed the presence
Although a number of mononuclear metal complexes of two species (the meso- and rac- isomers; readily identified
containing H-bonding sites have been described, examples with from the central CH2 resonance which is a singlet for the rac-
metallo-supramolecular architectures are rare.5 To achieve isomer and two doublets for the meso-isomer) in solution. The
directional control, two or more hydrogen bonds must be meso-isomer is the enthalpic product, while the rac-isomer is
formed between each component, yet building blocks contain- favoured entropically.6 Recrystallisation from acetonitrile by
ing multiple hydrogen bonding acceptors and donors are often the slow diffusion of diethyl ether afforded crystals of the meso-
associated with challenging covalent synthesis (and potential isomer suitable for X-ray crystallography. The structure (Fig. 1)
solubility problems). Our design employs ligands function- reveals the expected metallo-supramolecular box units. The
metal coordination does indeed create di- hydrogen bond sites
† Electronic supplementary information (ESI) available: Electronic Supple- and the boxes are linked together through pairs of hydrogen
mentary Information (ESI) available: full experimental details; character- bonds to give infinite chains of boxes (O–H…O 1.98 Å; O…O
isation data; crystallographic information; additional views and discussion 2.68 Å; •OHO 140°). The cavities of the boxes are filled with
of the solid state structures. See [Link] acetonitrile solvent molecules (see supplementary informa-
b308963k/ tion†).
DOI: 10.1039/b308963k

Fig. 1 Structure of the chains of cations observed in the structure of [Cu2(L1)2][PF6]2; hydrogens are omitted except those in the H-bonds

2666 CHEM. COMMUN., 2003 2666–2667 This journal is © The Royal Society of Chemistry 2003
Published on 08 October 2003. Downloaded by Institute of Chemistry, CAS on 6/30/2018 [Link] AM. View Article Online

Fig. 2 Structure of the chains of cations observed in the structure of [Cu2(L2)2][PF6]2; hydrogens are omitted except those in the H-bonds.

Fig. 3 Structure of the chains of cations observed in the structure of [Cu2(L2)2]Cl2; hydrogens are omitted except those in the H-bonds.

The corresponding copper(I) complex of L2 (which contains this structure each hydroxy acts as a hydrogen bond donor.
ethyl groups on the phenyls of the spacer units) was also Adjacent cations are connected through two such bridges and all
prepared. As expected the introduction of the ethyl groups leads hydroxys are involved in the hydrogen bonding network. The
to the formation of only the rac-isomer (double-helicate); Mass anions are now incorporated within the supramolecular chain
spectrometry confirms a dinuclear [Cu2(L2)2]2+ formulation and rather than lying outside it as in the other structures. Within the
NMR reveals a single solution species, even at low temperature, chains each cation possesses the same helicity (leading to chiral
in which the central CH2 resonance is a singlet. Recrystallisa- helical chains), while the helicity alternates between chains
tion of the hexafluorophosphate complex from acetonitrile by rendering the overall structure achiral.
diffusion of diethyl ether yielded suitable crystals. The X-ray We have demonstrated herein that a metal-directed assembly
crystal structure (Fig. 2) confirms the double-helical structure of process may be harnessed to create not only supramolecular
the cations. These double-helical cations are again linked into architectures but also to create multiple H-bond sites using
infinite chains through hydrogen-bonding interactions (O– readily prepared ligands bearing discrete H-bond units. These
H…O 1.89 Å; O…O 2.71 Å; •OHO 169°). However, in multiple H-bond sites may be used to aggregate the metallo-
contrast to the structure with L1, in this structure a single supramolecules into larger assemblies. Anions can compete
hydrogen bond links adjacent cations. The other hydroxy with the hydrogen bonding but this feature can be integrated
groups engage in hydrogen bonding to fluorine groups from the into the molecular design to yield arrays in which the anion is
anions (O–H…F 2.16, 2.26 Å; O…F 2.99, 3.09 Å; •OHF 166, incorporated rather than remote. We are currently exploring
169°). Within the chains the helicity of the cations alternates how to integrate further supramolecular interactions to design
rendering the chains achiral. more sophisticated assembly pathways based on multiple
The ‘interference’ of the anions in the hydrogen bonding recognition events.
motif might at first appear to be a potential problem for Support from EU Marie Curie Fellowships (A.L.; MCFI-
integrating hydrogen-bonding with assembly of cationic met- 2000-01003; F.T.; MCFI-2000-00403) is acknowledged.
allo-supramolecular architectures. While the interference could
potentially be circumvented by using anions without electro-
negative atoms, such as tetraphenylborate, such anions will
Notes and references
inevitably introduce alternate competing supramolecular inter- 1 J.-M. Lehn, Supramolecular Chemistry – Concepts and Perspectives,
actions (for example Dance7 has elegantly demonstrated the use VCH, Weinheim, 1995; Comprehensive Supramolecular Chemistry, Eds.
of tetraphenylborate in aryl crystal embraces). However the J. L. Atwood, J. E. D. Davies, J.-M. Lehn, D. D. MacNicol and F. Vogtle,
ability of anions to act as H-bond acceptors can be turned to our Pergamon: Oxford, 1996.
2 L. J. Childs, N. W. Alcock and M. J. Hannon, Angew. Chem., Int. Ed.,
advantage by incorporating this feature into the supramolecular 2001, 40, 1079–1081; L. J. Childs, N. W. Alcock and M. J. Hannon,
design; how this can be achieved is illustrated by using chloride Angew. Chem., Int. Ed., 2002, 41, 4244.
as the anion. 3 M. J. Hannon, C. L. Painting and W. Errington, Chem. Commun., 1997,
The comparatively small, spherical chloride anion has strong 1805.
potential to act as a hydrogen bond acceptor and can do so to 4 M. Vázquez, A. Taglietti, D. Gatteschi, L. Sorace, C. Sangregorio, A. M.
multiple hydroxy groups. Suitable crystals of the chloride salt González, M. Maneiro, R. M. Pedrido and M. R. Bermejo, Chem.
were obtained from methanol solution by diffusion of benzene. Commun., 2003, 1840.
The crystal structure (Fig. 3) again reveals double-helical 5 E. Breuning, U. Ziener, J.-M. Lehn, E. Wegelius and K. Rissanen, Eur.
cations linked into an infinite chain. However, in contrast to the J. Inorg. Chem., 2001, 1515; Z. Qin, M. C. Jennings and R. J. Puddephatt,
Chem. Commun., 2001, 2676.
hexafluorophosphate salt, the hydroxy units are not hydrogen 6 M. J. Hannon, C. L. Painting and N. W. Alcock, Chem. Commun., 1999,
bonded to each other but to chloride anions which bridge 2023; M. J. Hannon, C. L. Painting, J. Hamblin, A. Jackson and W.
between hydroxy groups (O–H…Cl 2.21, 2.28, 2.23, 2.50 Å; Errington, Chem. Commun., 1997, 1807.
O…Cl 3.04, 3.11, 2.99, 3.02 Å; •OHCl 171, 167, 151, 122°). 7 See for example: P. A. W. Dean, M. Jennings, U. Rajalingam, D. C.
Thus, rather than acting alternately as donors and acceptors, in Craig, M. L. Scudder and I. G. Dance, CrystEngComm, 2002, U1.

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