Article

Cite This: J. Am. Chem. Soc. 2019, 141, 15693−15699 pubs.acs.org/JACS

Perylene-Based Covalent Organic Frameworks for Acid Vapor

Sensing
Laura Ascherl,† Emrys W. Evans,‡ Jeffrey Gorman,‡ Sarah Orsborne,‡ Derya Bessinger,†
Thomas Bein,† Richard H. Friend,‡ and Florian Auras*,‡
†
Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU), Butenandtstraße 5-13, 81377
Munich, Germany
‡
Cavendish Laboratory, University of Cambridge, Cambridge CB3 0HE, United Kingdom
*
S Supporting Information
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ABSTRACT: Traditionally, the properties and functions of covalent organic

frameworks (COFs) are defined by their constituting building blocks, while the
chemical bonds that connect the individual subunits have not attracted much
attention as functional components of the final material. We have developed a
new series of dual-pore perylene-based COFs and demonstrated that their imine
bonds can be protonated reversibly, causing significant protonation-induced color
shifts toward the near-infrared, while the structure and crystallinity of the
frameworks are fully retained. Thin films of these COFs are highly sensitive
colorimetric acid vapor sensors with a detection limit as low as 35 μg L−1 and a
response range of at least 4 orders of magnitude. Since the acidochromism in our
COFs is a cooperative phenomenon based on electronically coupled imines, the COFs can be used to determine simultaneously
the concentration and protonation strength of nonaqueous acid solutions, in which pH electrodes are not applicable, and to
distinguish between different acids. Including the imine bonds as function-determining constituents of the framework provides
an additional handle for constructing multifunctional COFs and extending the range of their possible applications.

■ INTRODUCTION
Covalent organic frameworks (COFs) are two-dimensional1−3
popular imines, on the other hand, can enable electronic
communication across the bond but act as very strong
or three-dimensional4,5 crystalline, fully organic networks, in acceptors, causing extremely fast nonradiative quenching of
which the key physical properties, such as the type and energy excited states.18,20,28 Recently, strategies to overcome these
of optical transitions6,7 or the electrical conductivity,8−10 are adverse characteristics of imines via postsynthetic trans-
highly tunable. These materials can also be seen as a periodic formations into oxazoles, thiazoles, or quinolines have been
lattice of extremely well-defined pores.11−14 The environment developed.29−31 However, little effort has been undertaken
that a guest molecule encounters in these pores can vary over a thus far to make use of the imine bonds themselves and
wide range; e.g., it can be hydrophilic or hydrophobic or can employ them as a functional part of the final framework.
include different functional groups on the pore walls.15−17 Here we utilize the lone electron pair of the imine linkages
When constructing new COFs and defining their properties, as the function-determining moiety of a new series of two-
the focus lies traditionally on the choice of appropriate dimensional COFs. The COFs are based on a newly developed
building blocks, such as aryls,18,19 (fused) thiophenes,20−22 or perylene tetraaniline building block and adopt a star-shaped
other extended heteroarenes.23−25 The bond that connects dual-pore topology. Protonation of the imine bonds in these
them, however, is often considered a necessary evil. The materials causes significant absorption red-shifts and the
linkage chemistry is selected to be reversible enough to provide formation of protonation-induced absorption bands in the
the required self-healing capabilities during the COF synthesis near-infrared, while the structure and crystallinity of the
yet yield a sufficiently stable framework in order to avoid fast frameworks are fully retained. We find that the acidochromism
degradation during the intended application. depends on both acid strength and concentration, allowing us
Apart from these structural aspects, the bond is primarily
to use this effect for sensing and distinguishing between acids
meant to interfere as little as possible with the function of the
in solution and in the vapor phase. We demonstrate that
framework. In fact, the linkage chemistry is often regarded as
one of the limiting factors for potential applications of COFs, perylene COF thin films can serve as highly sensitive
especially in terms of their practicability in optoelectronics or colorimetric acid vapor sensors with a response range of at
electrochemical applications. Nonconjugated bonds such as least 4 orders of magnitude.
boronate esters have little impact on the adjacent building
blocks but impede in-plane electronic communication and Received: July 28, 2019
charge transport.26,27 Conjugated linkages such as the very Published: September 24, 2019

© 2019 American Chemical Society 15693 DOI: 10.1021/jacs.9b08079

J. Am. Chem. Soc. 2019, 141, 15693−15699
Journal of the American Chemical Society Article

Figure 1. Construction of the new perylene COFs. (a) The solvothermal co-condensation of the perylene tetraaniline with linear dicarbaldehydes
yields the star-shaped dual-pore Per-1P, Per-N, and Per-Py COFs. (b−d) Experimental PXRD patterns of the perylene COFs (black symbols).
Pawley refinements (red lines) provide a good fit with only minimal differences (green) between the experimental and the refined patterns. Bragg
positions are indicated by blue ticks. (e−g) Force-field-derived, Pawley refined structure models of the three perylene COFs. The Connolly surfaces
are calculated for a nitrogen-sized probe (r = 0.184 nm).

■ RESULTS AND DISCUSSION

While the range of tetradentate aldehyde building blocks for
The new perylene COFs were synthesized via solvothermal
co-condensation of Per(NH2)4 with the phenylene-, naph-
2D COFs has expanded significantly over the past years, tetra- thalene-, and pyrene-based dicarbaldehydes (see the Support-
amines are still limited to only three building blocks, i.e., the ing Information, section B for experimental details).
pyrene, ethene, and porphyrin tetraanilines.12,16,26 In order to The powder X-ray diffraction (PXRD) patterns of the COFs
extend this range toward larger aromatic units, we have show sharp reflections and several well-resolved higher-order
developed a perylene-based building block. The 2,5,8,11-
tetrakis(4-aminophenyl)perylene (Per(NH2)4) generates star- reflections (Figure 1b−d). Due to the very large unit cells of
shaped COFs with small trigonal and large hexagonal pores these COFs, the overlap between some reflections even at low
(Figure 1). diffraction angles is unavoidable. The COFs were indexed and
15694 DOI: 10.1021/jacs.9b08079
J. Am. Chem. Soc. 2019, 141, 15693−15699
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Figure 2. Protonation of the Per-N COF with TFA vapor. (a) The imine-linked bridges of the Per-N COF can be protonated stepwise, causing a
fully reversible color change from yellow to dark brown. (b) Absorption spectra of a Per-N COF film upon protonation in TFA vapor of increasing
concentration (green to red lines). The COF film has a response range of at least 4 orders of magnitude, and the protonation can be fully reversed
by exposing the protonated COF to triethylamine vapor (gray dashed line). (c) Absorption difference between the protonated and fully
deprotonated COF showing a protonation-induced absorption band across the visible and near IR range, accompanied by a bleach band in the blue
and UV. Inset: absorption difference spectra normalized to their respective maximum. The absorption feature formed at low TFA concentrations
peaks at 500 nm with almost no absorption above 600 nm. At higher acid concentrations, however, an additional absorption feature develops in the
600−800 nm region. We attribute these two features to the monoprotonated and the bisprotonated imine-linked bridges, respectively (see
discussion below). Abbreviations: TFA = trifluoroacetic acid.

Pawley-refined in the hexagonal space group P6 with three deprotonation (Figure 2a). The protonated perylene, pyrene,
symmetry-equivalent perylenes per unit cell (Figure 1e−g). and triazine COFs can be stored in humid air for several hours
For comparison purposes, we also synthesized a range of without any noticeable degradation. Only the 4PE-TT COF,
COFs based on the literature-known tetraphenylpyrene,7,16,18 where the steric stabilization is reduced due to its twisted
tetraphenylethene,3,12 and triphenyltriazine32 building blocks. imine-linked bridges and significantly larger layer spacing (4.6
The syntheses and structures of these COFs are shown in the nm vs ca. 3.5 nm for the other COFs), is unstable toward
SI, sections B and D. humidity when protonated. A video showing the repeated
In order to facilitate the spectroscopic analysis and protonation and deprotonation of a pyrene COF film is
application as sensors, the COFs were also grown as thin supplied in the SI.
films on fused silica, sapphire, or indium tin oxide coated glass The protonation of the imine bonds can be achieved by
substrates (see the SI, section B for experimental details). 2D exposing the COF powders or thin films to acid solutions or
grazing-incidence wide-angle X-ray scattering (GIWAXS) vapors and can be followed by infrared spectroscopy (SI,
measurements confirm that the films consist of the crystalline Figure S7). We observe the appearance of the CNH+
COFs (SI, Figure S4). For the perylene COFs, we observe that stretching vibration around 1650 cm−1, accompanied by an
the intensities of the hk0 reflections are distributed almost attenuation of the imine CN stretching mode around 1610
evenly across semicircles with only slightly higher intensities cm−1.36
close to the substrate horizon, indicating that these COF films The lowest-energy optical transitions of imine-linked COFs
are polycrystalline with random crystallite orientation (SI, have significant charge-transfer character with the ground-state
Figure S4-1). This is in sharp contrast to the other COFs in electron density being distributed across the frameworks, while
this study and other reported COF films,33,34 which are highly the first singlet excited state is more localized on the imines
textured with their respective crystallographic a−b planes (SI, Figure S14). Since the protonated imines are stronger
parallel to the substrate. We attribute this random orientation electron acceptors than their free-base counterparts, the
to the significantly higher reactivity of the Per(HN2)4 building energies of these transitions are lowered, leading to red-shifted
block compared to the pyrene, ethene, or triazine anilines. The absorption and emission spectra. Most COFs are constructed
increased reactivity causes a rapid growth of the initially with two electronically coupled imines per bridge unit. In this
formed nuclei on the substrate without the typical equilibrium case, the simultaneous protonation of both imines increases
between imine condensation and dissolution that provides the the charge transfer character even further and enables an
selectivity for a−b-oriented domains. An additional factor additional stabilization via quinoidal resonance structures.
could be nuclei that form in the reaction mixture and are For the perylene COF series, we observe a color change
subsequently incorporated into the growing COF film. The from greenish-yellow to dark brown, caused by the appearance
resulting COF films, however, are optically transparent and of a protonation-induced absorption band in the 450−800 nm
homogeneous with only minimal light scattering. region that is accompanied by a bleach band below 450 nm
The nitrogen lone pair of imines can be protonated by (SI, Figure S5-1). Similar color shifts are observed for the other
sufficiently strong acids,35 but this process typically leads to COFs (SI, Figures S8 and S14a).
their decomposition if small amounts of water are present. We In their free-base form, the perylene COFs possess a red
found, however, that the close-packed structures of 2D COFs (Per-1P and Per-N COFs) or yellow (Per-Py COF) photo-
provide sufficient stabilization to render them stable against luminescence (PL) with comparably long PL lifetimes (SI,
hydrolysis and enable the fully reversible protonation and Figures S5-2 and S6). If protonated, however, the PL of the
15695 DOI: 10.1021/jacs.9b08079
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Figure 3. Protonation of pyrene COF films with acid solutions. (a) Chemical structure of the Py-TT COF. The structures of the Py-1P and the Py-
1POH COFs are shown in the SI, section B. (b) Absorption changes of the Py-TT COF film upon protonation with TFA solutions of various
concentrations in 1,4-dioxane. The protonation can be fully reversed by neutralization with Et3N (gray dashed line). (c) Plot of the absorption
difference between the protonated and the nonprotonated Py-TT COF showing the absorption features of the monoprotonated bridge (see
discussion below). (d) Evolution of the main absorption bands of the pyrene COFs, determined at their respective maxima (Py-TT COF: 578 nm,
Py-1P COF: 544 nm, Py-1POH COF: 590 nm). While the absorption change of the Py-TT and Py-1P COFs follows a logarithmic dependence on
the acid concentration, the protonation of the Py-1POH COF is considerably retarded due to the −OH···N hydrogen bonds. (e) Protonation of
the Py-TT COF with different acid solutions. TFA and TCA solutions produce selectively the monoprotonated bridge unit with a characteristic
absorption band between 550 and 750 nm. The considerably stronger MsOH generates a much stronger absorption band which extends further
into the IR, indicating the formation of the bis-protonated species. Insets: photographs of the deprotonated, monoprotonated, and bis-protonated
Py-TT COF. Abbreviations: TCA = trichloroacetic acid, TFA = trifluoroacetic acid, MsOH = methanesulfonic acid.

Per-Py COF is shifted drastically from 570 nm to about 1000 TFA concentrations, whereas at higher TFA concentrations
nm and is greatly reduced in intensity. The emission from the also the bis-protonated state (600−800 nm absorption) is
other protonated COFs is below the detection limit of our IR formed. The stepwise protonation will be discussed in more
detectors. detail below.
Building on these initial observations, we investigated the The protonation can be fully reversed by exposing the COF
potential of a Per-N COF film as an acid vapor sensor. The to triethylamine vapor, followed by washing in acetonitrile to
COF film was placed in a sealed cuvette, and a defined acid remove the triethylammonium salt (Figure 2b,c, dashed gray
atmosphere was generated by evaporating 1 μL of a line). To conclude, the Per-N COF acts as a very sensitive
trifluoroacetic acid (TFA) solution in tetrahydrofuran, yielding colorimetric acid vapor sensor with a low detection limit and a
acid vapor concentrations between 35 μg L−1 and 110 mg L−1. response range of at least 4 orders of magnitude.
Even the lowest acid concentration causes a measurable change For a more detailed analysis of how the COF protonation
in the absorption spectrum with protonation-induced proceeds, we focus on a series of the well-established pyrene
absorption and bleach bands extending from 440 to 800 nm COFs (Figure 3a). The Py-TT COF is a donor−acceptor
and below 440 nm, respectively (Figure 2b,c). These bands variant of the archetypical Py-1P COF that forms particularly
become more intense with increasing acid vapor concentration, crystalline films.7,18 In the Py-1POH COF, the hydroxy groups
without any saturation effects. We observe, however, the provide an additional stabilization of the structure via
gradual evolution of an additional IR component as the acid hydrogen bonding to the adjacent imine nitrogens.16,37
vapor concentration is increased (Figure 2c, inset). We Combining the pyrene tetraaniline with the pyrene tetraalde-
attribute these spectral changes to the protonation of only hyde yields the Py-Py COF with only one imine bond per
one of the two imines per bridge (500 nm absorption) at low bridge (SI, Figure S12a).7
15696 DOI: 10.1021/jacs.9b08079
J. Am. Chem. Soc. 2019, 141, 15693−15699
Journal of the American Chemical Society Article

If the protonation is carried out using TFA solutions in acid solutions. Indeed, only one protonated state is formed
dioxane rather than acid vapor, we observe a gradual color regardless of the protonation strength of the acid.
change of the Py-TT COF from initially orange to dark brown In addition to the COF films being very sensitive acid vapor
due to the appearance of a strong absorption band between sensors, the balance between the mono- and bisprotonated
500 and 750 nm (Figure 3b,c). An additional absorption band states provides additional information about the respective acid
is formed at 450 nm, accompanied by a bleach band around mixture. COF films could be employed as colorimetric probes
370 nm. The intensity of the absorption and bleach bands for determining simultaneously the concentration and the
follows a logarithmic dependence on the acid concentration protonation strength of nonaqueous acid solutions, which are
(Figure 3d, red triangles). The spectral features, however, incompatible with standard pH electrodes. The close-packed
remain unaffected by the acid concentration, suggesting that crystalline COF lattice provides the stability, molecular-scale
under these protonation conditions only a single, well-defined porosity, and easy read-out required for reliable sensing.
protonated state is formed. The protonation can be fully
reversed by immersing the COF film in a dilute Et3N solution.
During the protonation and subsequent deprotonation, the
■ CONCLUSION
We have developed a series of star-shaped dual-pore perylene-
crystallinity and porosity of the COFs and COF films are fully based COFs and have demonstrated that their imine bonds can
retained (SI, Figure S11). be reversibly protonated, causing significant color shifts.
The protonation behavior of the Py-1P COF is very similar, Protonation of the phenylene−NCH−bridge−HCN−
whereas the protonation of the Py-1POH COF is significantly phenylene subunits proceeds in a two-step process with the
delayed, highlighting its stabilization via −OH···N hydrogen second protonation requiring significantly stronger acids. The
bonds that counteract the imine protonation (Figure 3d and mono- and the bisprotonated species have distinct absorption
SI, Figure S8). features in the red and near-infrared spectral regions, enabling
When comparing the absorption spectra obtained upon the COFs to act as colorimetric sensors for simultaneously
protonating the COFs with dilute solutions of various acids, determining the acid strength and concentration in non-
however, we notice considerable differences (SI, Figure S10). aqueous solutions where pH electrodes are not applicable.
The weakest acids (acetic acid and chloroacetic acid) do not Moreover, the COF films are highly sensitive acid vapor
cause any considerable protonation. The stronger halogenated sensors with a very low detection limit and a response range of
acetic acids (dichloroacetic acid, trichloroacetic acid, TFA) can at least 4 orders of magnitude. By using the imine bond itself as
monoprotonate the Py-TT and Py-1P COFs (and the Py-1POH a function-determining moiety, we have provided an additional
COF to some degree), producing the spectral features handle for constructing functional COFs for a broad range of
discussed above. Exposing the COFs to these acids at higher applications.
concentrations yields the same absorption signatures with
higher intensities. The even stronger p-toluenesulfonic acid
and methanesulfonic acid, however, do not only produce more
■
*
ASSOCIATED CONTENT
S Supporting Information
intense absorption bands than the other acids at the same The Supporting Information is available free of charge on the
concentration but also give rise to significantly different ACS Publications website at DOI: 10.1021/jacs.9b08079.
spectral features that extend much further into the IR. The Experimental methods, synthetic procedures, structure
same IR-extended absorption bands can also be obtained with analysis and additional spectroscopic data (PDF)
saturated TFA vapor or other strong acids (SI, Figure S13) or
Video of the reversible protonation (MPG)
TFA solutions in solvents that are very poor hydrogen bond
Per-1P COF Pawley-refined structure model (CIF)
acceptors (SI, Figure S9),38 suggesting that their formation
Per-N COF Pawley-refined structure model (CIF)
depends on the protonation strength of the respective acid
mixture rather than the choice of the acid anion. Per-Py COF Pawley-refined structure model (CIF)
The observations above strongly suggest that the proto- Tz-TT COF Rietveld-refined structure model (CIF)
nation proceeds in two distinct steps with characteristic
absorption bands extending to about 750 nm and beyond 1000
nm, respectively, in the case of the Py-TT COF. No
■ AUTHOR INFORMATION
Corresponding Author
intermediates or gradual absorption shifts are observed. We *[email protected]
attribute these steps to the mono- and the bisprotonation of ORCID
the two electronically coupled imines within one phenylene− Emrys W. Evans: 0000-0002-9092-3938
NCH−bridge−HCN−phenylene unit (Figure 3e). The Jeffrey Gorman: 0000-0002-6888-7838
first protonation can be achieved with a variety of acid
Thomas Bein: 0000-0001-7248-5906
solutions. However, this monoprotonation reduces the basicity
of the neighboring imine, and thus considerably more Richard H. Friend: 0000-0001-6565-6308
protonation strength is required for the second protonation. Florian Auras: 0000-0003-1709-4384
This cooperative phenomenon involving electronically coupled Notes
The authors declare no competing financial interest.

■
imines sets our COFs apart from previous examples of
acidochromic framework materials, which rely on isolated
acidochromic building blocks.39,40 ACKNOWLEDGMENTS
The assignments of the spectra to the mono- and This project has received funding from the European Research
bisprotonated imine bridges are further supported by Council (ERC) under the European Union’s Horizon 2020
comparison with the Py-Py COF (SI, Figure S12). Since this research and innovation programme (grant agreement no.
framework contains only one imine bond per bridge, we do not 670405). The research leading to these results has received
expect to observe the second protonation step with stronger funding from the European Research Council under the
15697 DOI: 10.1021/jacs.9b08079
J. Am. Chem. Soc. 2019, 141, 15693−15699
Journal of the American Chemical Society Article

European Union’s Seventh Framework Programme (FP7/ (17) Xu, H.; Gao, J.; Jiang, D. Stable, crystalline, porous, covalent
2007-2013/ERC grant agreement no. 321339). We thank Prof. organic frameworks as a platform for chiral organocatalysts. Nat.
Matthias Thommes for fruitful discussions. Chem. 2015, 7, 905−912.

■
(18) Auras, F.; Ascherl, L.; Hakimioun, A. H.; Margraf, J. T.;
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