A Heteromeric Carboxylic Acid Based Single-Crystalline Crosslinked Organic Framework

Article abstract of DOI:10.1002/anie.202109987

The development of large pore single-crystalline covalently linked organic frameworks is critical in revealing the detailed structure-property relationship with substrates. One emergent approach is to photo-crosslink hydrogen-bonded molecular crystals. In

Full text of DOI:10.1002/anie.202109987

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Accepted Article
Title: A Heteromeric Carboxylic-acid-based Single Crystalline
Crosslinked Organic Framework
Authors: Rongran Liang, Jayanta Samanta, Baihao Shao, Mingshi
Zhang, Richard Staples, Albert Chen, Miao Tang, Yuyang
Wu, Ivan Aprahamian, and Chenfeng Ke
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COMMUNICATION
A Heteromeric Carboxylic-acid-based Single Crystalline
Crosslinked Organic Framework
[
a]
[a]
[a]
[a]
[b]
Rongran Liang, Jayanta Samanta, Baihao Shao, Mingshi Zhang, Richard J. Staples, Albert D.
[
a]
[a]
[c]
[a]
[a]
Chen, Miao Tang, Yuyang Wu, Ivan Aprahamian* , and Chenfeng Ke*
[
a]
Dr. R. Liang, Dr. J. Samanta, Dr. B. Shao, M. Zhang, A. D. Chen, M. Tang, Prof. I. Aprahamian, Prof. C. Ke
Department of Chemistry
Dartmouth College
6128 Burke Laboratory, Hanover, New Hampshire, 03755, United States
E-mail: chenfeng.ke@dartmouth.edu; ivan.aprahamian@dartmouth.edu
Dr. R. J. Staples
Department of Chemistry
[
[
b]
c]
Michigan State University
578 S. Shaw Lane, Michigan State University, East Lansing, MI, 48824, United States
Dr. Y. Wu
IMSERC, Department of Chemistry
Northwestern University
2145 Sheridan Road, Evanston, Illinois 60208, United States
Supporting information for this article is given via a link at the end of the document.
Abstract: The development of large pore single-crystalline covalently
linked organic frameworks is critical in revealing the detailed structure-
property relationship with substrates. One emergent approach is to
photo-crosslink hydrogen-bonded molecular crystals. Introducing
complementary hydrogen-bonded carboxylic acid building blocks is
promising to construct large pore networks, but these molecules often
form interpenetrated networks or non-porous solids. Herein, we
introduced heteromeric carboxylic acid dimers to construct a non-
interpenetrated molecular crystal. Crosslinking this crystal precursor
with dithiols afforded a large pore single-crystalline hydrogen-bonded
due to undesired side-on hydrogen-bonding interactions[9b]
formed in the solid-state, making it challenging to construct
C
H OFs with large pores.
One attempt to address the challenge was to introduce self-
complementary hydrogen-bonding functional groups such as
carboxylic acids[12] to direct the network topology. However, the
framework architectures formed by homo-carboxylic acid
derivatives often encounter undesired network interpenetrations
and they are susceptible to even a slight structural modification.[
The problem is well illustrated in the various interpenetrated
networks generated by 1,3,5-tris(4-carboxyphenyl)benzene
13]
crosslinked organic framework H
revealed H OF-101 as an interlayer connected hexagonal network,
which possesses flexible linkages and large porous channels to host
hydrazone photoswitch. Multicycle ZE-isomerization of the
hydrazone took place reversibly within H OF-101, showcasing the
potential use of H OF-101 for optical information storage.
C
OF-101. X-ray diffraction analysis
C
a
C
C
Developing covalently connected porous organic framework
materials with high crystallinity,[1] good chemical stability,[2] and
large porosity[3] is highly desired to not only establish precise
structure-property relationships between porous materials and
sorbates, but also advance their practical applications in gas
separation,[4] catalysis,[5] and optoelectronics.[6] While one
approach of fine-tuning the reversible reactions to obtain single-
crystalline covalent organic frameworks[7] (COFs) has been
demonstrated successful,[1b] the small crystal sizes of COFs often
limit their diffraction data quality to fully unveil the detailed atomic
level information.[8] Another emerging approach to generate
single-crystalline porous organic materials is covalently
crosslinking hydrogen-bond pre-organized molecular crystals.
This approach generates
crosslinked organic framework (H
combined the advantages of hydrogen-bonded organic
a
family of hydrogen-bonded
OF) materials,[9] which
C
frameworks[ (HOFs) and COFs. To date, reported H
10]
[11]
C
OFs are
Figure 1. (a) Illustration of the heteromeric assembly of carboxylic acid
constructed using non-complementary hydrogen-bonding motifs
such as diallyl- and dipropargyl-diaminotriazines (DATs). The
formed hydrogen-bonded networks possess limited pore sizes
derivatives of mis-matched sizes and pK
interpenetrated OF-101 through co-crystallization of size-mismatched
monomers followed by a thiol-ene single-crystal to single-crystal transformation.
a
values. (b) Synthesis of the non-
H
C
1
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(
TCPB) derivatives in the solid-state (Scheme S3).[14] Herein, we
formed intermolecular hydrogen bonds with the upper layer
allylether (OH•••O = 2.46 Å, Figure 2a) and the carboxylic acid of
M1 (OH•••O = 1.99 Å). The typical carboxylic acid dimer was not
formed in the solid-state, and M1 stacked into 1D columns
through interlayer hydrogen bonding interactions. These M1
columns are packed hexagonally via van der Waals interactions
with narrow 1D porous channels (Figure 2a). The allylethers of
M1 prevented the formation of carboxylic acid dimers in the solid-
state, which confirmed that the substitution of the TCPB
drastically altered its solid-state superstructure.
introduce, for the first time, heteromeric size-mismatched
carboxylic acid derivative M1 and trimesic acid TA to construct a
single-crystalline covalently linked organic framework H
which features large pore and non-interpenetrated hydrogen-
bonded network (Figure 1). H OF-101 was synthesized through
a single-crystal to single-crystal (SCSC) transformation[15] from a
D hexagonal hydrogen-bonded network through the thiol-ene
C
OF-101,
C
2
crosslinking. Compared to electron diffraction (ED) data that
mostly reveal the framework topology for COFs,[8,16] the high-
quality single-crystal X-ray diffraction data of H
C
OF-101 enabled
To prevent the undesired close-packing of M1 and direct its
solid-state assembly to form a large porous hydrogen-bonded
network, we sought to introduce a carboxylic acid-based filler
the precise determination of the pore sizes with flexible
crosslinkages connecting a large pore 2D network in four different
interlayer ways. The large 1D porous channels (D = 1.4 nm,
3
molecule that features a similar C geometry but of different size.
Figure 1b) of H
C
OF-101 was not only capable of adsorbing a
Surprisingly, no prior example has yet shown heteromeric co-
crystallization of two carboxylic acid derivatives in the
construction of porous hydrogen-bonded network. Limited
successful examples of non-porous heteromeric dimerization of
benzoic acid derivatives with electron-donating and electron-
withdrawing groups[12,17] suggested that introducing a filler
hydrazone photoswitch of nearly one nanometer in size but also
enabled the hydrazone photo-isomerizations in these channels.
In multi-cycle writing-erasing experiments, the hydrazone-loaded
H OF-101 demonstrated switchable solid-state fluorescent
C
emissions, manifesting the potential use of this platform as a
solid-state information storage device.
Triallylether-based monomer M1 was synthesized from 1,3,5-
tribromobenzene in four steps with 53% overall yield (see the
Supporting Information). Slow vapor diffusion of methanol into the
molecule of different pK
carboxylic acid dimerization against homo-self-sorting.
The pK of M1 was measured as 8.9 ± 0.1, 9.9 ± 0.1, and 10.9
a
to M1 would favor the heteromeric
a
± 0.2 in MeOD at 298 K using 1H NMR spectroscopy (Figure
S1).[18] We chose trimesic acid TA as the template molecule to
form heteromeric carboxylic acid co-assembly with M1 because
1
,4-dioxane solution of M1 afforded M1crystal that is suitable for
single-crystal X-ray diffraction (SCXRD) analysis. M1crystal
̅
crystallized in the P3 space group, and three of the carboxyphenyl
of its different pK
a
(3.1, 3.9 and 4.7) to M1 analog 2-
propoxybenzoic acid (4.2) in water.[ The pK
19]
of TA in MeOD
rings are rotated out of the plane to the central phenyl ring with a
dihedral angle of 46 (Figure 2a). The carboxylic acids of M1
a
o
were measured as 8.0 ± 0.1, 9.4 ± 0.1, and 10.6 ± 0.1,
Figure 2. (a) Crystal structures of M1crystal connected via intermolecular hydrogen bonds. (b) PXRD profiles of (co-)crystals generated at different M1/TA feeding
ratios. (c) Crystal structures of M1-TAcrystal. Top: asymmetric unit, middle: an image of the crystal, bottom: packed structures viewed along the a/b plane and c-axis,
hydrogens were omitted for clarity.
2
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respectively (Figure S2). When a less-than-stoichiometric amount
of TA was added to M1, powder X-ray diffraction (PXRD, Figure
2
b) experiments showed a self-sorted crystallization outcome‒
only M1crystal was formed. When TA/M1 ≥ 1:1, a new crystalline
phase emerged and remained the same at higher TA/M1 ratios.
Single crystals of this new crystalline phase were obtained, and
SCXRD analysis revealed that M1 and TA co-crystallized in a 1:1
ratio in the P6
5
space group with unit cell parameters of a = b =
2
4.0075(2) Å, c = 19.5118(2) Å, α = β = 90, γ = 120. Heteromeric
carboxylic acid dimers were formed between M1 and TA,
affording a 2D hexagonal hydrogen-bonded network. This result
suggested that, when TA reached over stoichiometric amount to
a
M1, the more acidic carboxylic acid group of TA (pK = 8.4) could
stabilize the heteromeric carboxylic acid dimer formed between
M1 and TA. Allylether moieties of M1 were crystallographically
disordered with equal probabilities on either side of the
carboxyphenyl groups due to the phenyl-phenyl free rotations
(
Figure 2c). The pore size of M1-TAcrystal is measured to be 16 Å
when accounting for the allylethers, which is smaller than the d =
1 Å calculated from the (100) diffraction (Figure 2b-c). The
2
carboxyphenyl groups of M1 were found to be nearly co-planar
with the central phenyl ring, with small dihedral angles of 6.8,
9
.6, and 27.9, respectively. This conformation of M1 enabled
alternating TA/M1 π-π stacking along the c-axis (centroid to
centroid, 3.66-3.73 Å). Interestingly, this alternating M1 and TA
stacking is not perfectly eclipsed, and there are small offsets
between the phenyl rings of different layers (Figure 2c), which
provide some structural insights to previously proposed eclipsed
2
D COFs.[3a,3c,20] The M1-TA co-crystal consists of 47% void
space as 1D porous channels, which is sufficiently large for
ethanedithiol (EDT, HSCH CH SH) diffusion. Multiple pairs of allyl
2
2
groups (Table S4) were found within the suitable distances for
EDT crosslinking.
Single crystals of M1-TAcrystal were soaked in MeCN solutions
with various concentrations of EDT in the dark for 4 d to reach
equilibrium before they were irradiated under UV light. The
crystals were washed extensively and then soaked in hot,
1
degassed DMSO-d
6
(140 C) before H NMR analysis at 25 C.
The TA moiety was removed from the crystal and dissolved in
DMSO-d
6
(Figure S3), and its proton signals were used as an
OF-101. (b) Stacked 13C NMR spectra (298 K) of
C
Figure 3. (a) Synthesis of H
M1/TAcrystal dissolved in DMSO-d
Stacked 1H NMR spectra (298 K) of M1 in DMSO-d
01 in DCl/DMSO-d
1
internal H NMR reference. A stoichiometric EDT/allyl = 1:2
reaction would afford fully crosslinked H OF-101 (Figure 3a), but
C
reactions that drifted from the stoichiometry would afford
oligomeric species. Experimentally, these species were extracted
6
and H
C
OF-101 recorded in the solid-state. (c)
6
and fully digested H OF-
C
1
6
.
6
from the crosslinked crystals using hot DMSO-d , and they were
completely into soluble species in DCl-DMSO-d
6
solution at 75 C.
observed at higher EDT feeding concentrations (Figure S3).
Decreasing the EDT concentrations to 60-203 μmol/mL resulted
in extensive crosslinking of M1, as no appreciable amount of
soluble species was extracted according to 1H NMR analysis
1
H NMR analysis (Figure 3c) showed only trace amounts of proton
signals at 4.8-6.2 ppm, which may be attributed to trace amounts
of hydrolyzed allylethers (Figure S7).
C
Transparent crystals of H OF-101 retained the needle-like
(
Figure S3). After reaction optimization (Table S2), a close-to-
stoichiometric crosslinking (EDT/allyl = 1:1.9) was achieved with
OF-101 as revealed by elemental analyses. Further evidence
supports the successful crosslinking of H OF-101. In the FT-IR
spectrum of H OF-101 (Figure S5), bending vibrations of the allyl
groups at 995 cm (‒CH=) and 927 cm (=CH
the solid-state 13C CPMAS NMR spectrum of H
morphology (Figure 4a). Its symmetry was reduced to the
monoclinic C2 space group due to the generated dithioethers,
with the unit-cell parameters of a = 24.0134(2), b = 41.5667(2), c
H
C
C
=
13.42270(10) Å, α = γ = 90, β = 104.2590(10). The hydrogen-
C
bonded TCPB and TA skeleton was well refined in the SCXRD
analysis (Figure 4a), and it remained nearly identical to the parent
M1-TAcrystal (Figure S13). The dithioether crosslinkages inherited
the disorders from the parent M1-TAcrystal, and they were found at
both sides of the carboxyphenyl groups. Fortunately, high-quality
synchrotron SCXRD data allowed us to model most of the
crosslinkages despite some of them overlapping (Figure 4b).
-1
-1
2
) disappeared. In
OF-101, carbon
C
resonances of C11-C13 at ~30 ppm (Figure 3b), attributed to
thioether moieties, were identified. Due to several overlapped
carbon signals at 120-135 ppm in the solid-state 13C NMR, we
sought to confirm the complete consumption of allylethers through
C
a digestion experiment. H OF-101 crystals were digested
3
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Figure 4. (a) Single-crystal structure of H
Dissected sections of H OF-101, illustrating different interlayer crosslinkages. (c) PXRD profiles of H
isotherms of H OF-101.
C
OF-101 viewed along the c-axis (left) and its highlighted pore surfaces (right). Inset: an image of H
C
OF-101 crystals. (b)
C
C
OF-101 soaked in various solvents. (d) Vapor sorption
C
In H
C
OF-101, the dithioether crosslinkage A was found to
size and chemical environment of the 1D porous channels in
H
C
OF-101, and more broadly post-modified 2D COFs.[21]
connect M1 in the non-adjacent 1,4-layers (Figure 4b), reflecting
the distances between two allyls that are 7.1 Å apart in M1-TAcrystal
Table S4). Linkages C and D were found to connect two allyl
Secondly, each allyl group has two or more nearby allyls for
crosslinking, and the large 1D porous channel allows the
crosslinking to take place extensively. This result highlights the
benefit of large pore, because limited pore size could severely
impact the extensiveness of crosslinking as evident in the
(
groups in 1,3-layers that are 8.6 and 7.2 Å apart in M1-TAcrystal
,
respectively. Linkages B consist four possible 1,2- and 1,3-layer
linkages, which are super-imposed crystallographically (Figure
S15). These dithioether moieties were weakly associated to the
pore surfaces along the 1D channels. The pore size and void
synthesis of
significantly enhanced the chemical stability of H
H
C
OF-4.[9b] These covalent crosslinkages
OF-101 in
C
space of H
respectively (Figure 4a). Comparison between the clearly
modeled multiple linkages in H OF-101 and the conformations of
C
OF-101 were measured as ~14 Å and 27%,
various solvents as revealed by the PXRD analysis (Figure 4c). In
comparison, the solid state structure of M1-TAcrystal was disrupted
upon exposing to various solvents (Figure S25-26). The
C
allylethers in M1-TAcrystal (Figure S13) revealed two key factors to
allow extensive thiol-ene crosslinking, despite allylethers are
randomly distributed at each side of the carboxyphenyl group in
M1-TAcrystal. Firstly, the allyl ether moieties are reasonably
2 C
supercritical CO -activated H OF-101 demonstrated good vapor
uptake[22] (Figure 4d and S26a) of water, methanol, and toluene
3
as 91, 92, and 105 cm /g (P/P
0
= 0.9) at 297 K, respectively.
C
H OF-101 is sufficiently large to
The pore size of
accommodate a fluorescent photoswitch Z-H1 (Figure 5a),
which features a cross-section width of 9.5 Å. Immersing H OF-
101 in an acetone/MeOH solution of hydrazone Z-H1 afforded
orange-colored H OF-101•Z-H1 with an uptake capacity of 0.15
[
23]
C
dynamic for efficient crosslinking during the H OF-101 synthesis,
because the formed dithioethers adopt different conformations
compared to their precursors. This result provides detailed
structural information of the flexible auxiliaries in changing the
C
C
4
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
0.022 mmol/g. Z-H1 emits at λem = 560 nm in toluene, but its
network and the configured conformations of rather flexible
emission is red-shifted to 620 nm in crystalline form because of
C
interlayer crosslinkages. H OF-101 demonstrated superior
chemical stability compared to its molecular crystal precursor, and
its permanent porosity was confirmed by vapor sorption analysis.
By including a photoswitch into H OF-101, a solid-state inclusion
C
material with switchable fluorescent emissions was obtained,
which is not possible in the neat crystal of the hydrazone. Overall,
our work not only successfully introduced heteromeric carboxylic
acid for the construction of porous crystalline network for the first
time, this method also demonstrated a practical way to suppress
network interpenetration. The detailed atomic level structure
information of H
sorbents, enabling the formation of hydrazon•H
C
OF-101 allowed us to precisely identify suitable
OF-101 as a
C
solid-state potential optical information storage device.
Acknowledgements
This work is supported by the National Science Foundation (NSF)
CAREER award (DMR-1844920) and the Beckman Young
Investigator Program. I. A. thanks the NSF MSN program (CHE-
Figure 5. (a) Structure of a hydrazone switch H1. (b) Solid-state fluorescence
emission spectra of H
C
OF-101•Z-H1 before and after 442 nm irradiation (λex
=
470 nm). (c) Multicycle patterning and erasing experiments performed on an
H
C
OF-101•Z-H1 crystal strip (9  1.5 mm). Fluorescent images were recorded
1
807428). C.K., R.L. acknowledges support from the NSF
under 365 nm light.
EPSCoR-1757371. J.S., C.K. thanks the American Chemical
Society Petroleum Research Fund (58377-DNI10). Funding for
the Single Crystal X-ray diffractometer at MSU was provided by
the MRI program by the NSF under Grant No. 1919565. This
research used resources of the Advanced Photon Source and the
Advanced Light Source, which are DOE Office of Science User
Facility under contract no. DE-AC02-06CH11357 and DE-AC02-
its head-to-tail packing.[23]
Figure 5b) in the solid-state upon 470 nm excitation, similar to
what is observed in the solution. Moreover, the large pore size of
C
H OF-101•Z-H1 emits (λem = 575 nm,
C
H OF-101 allows an effective Z- to E-H1 photoisomerization upon
4
42 nm irradiation with a photostationary state (PSS442) of 70%
0
5CH11231. Professor Yuebiao Zhang at Shanghai Tech
E-H1. This observation contrasts with what happens in the
crystalline form of Z-H1, where no appreciable isomerization was
observed even after prolonged photoirradiation. Clearly, the
University and Professor Omar Farha at Northwestern University
for helpful discussions.
inclusion of Z-H1 in H
solution rather than in its neat crystalline state.
The photoswitching of H OF-101•Z-H1 is accompanied with a
fluorescent color change from yellow to greenish-blue, which
results from the emission of H OF-101 with minor contributions
from the remaining Z-H1 at PSS442 (E-H1 is non-emissive).
Reverse E→Z photoisomerization of H1 in H OF-101 takes place
upon photoirradiation with 375 nm light or heating at 95 C. The
reversible solid-state switching of H OF-101•H1 enabled us to
use it in multicycle solid-state photo-patterning. When a strip of
OF-101•Z-H1 crystals was irradiated at 442 nm under a photo-
mask, the mask pattern was written into the solid-state material
Figure 5c). This pattern was erased upon heating at 95 C,
C
OF-101 makes H1 behave like it does in
Keywords: heteromeric carboxylic acid dimer • hydrogen-
bonded crosslinked organic framework • photo-switch • single-
crystalline porous organic material • single-crystal to single-
crystal transformation
C
C
C
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C
H OF-101 was synthesized. High-quality single-crystal diffraction
1
data revealed the architecture of H OF-101 as a 3D crosslinked
C
5
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COMMUNICATION
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Angewandte Chemie International Edition
10.1002/anie.202109987
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Table of Contents
Heteromeric dimer inhibited interpenetration. A large pore single-crystalline hydrogen-bonded crosslinked organic framework was
synthesized through heteromeric monomers co-crystallization followed by thiol-ene crosslinking. The crosslinked porous crystals
featured large pores to host a hydrazone switch for solid-state photo-patterning.
7
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