Docking Strategy To Construct Thermostable, Single-Crystalline, Hydrogen-Bonded Organic Framework with High Surface Area

Article abstract of DOI:10.1002/anie.201805472

Enhancing thermal and chemical durability and increasing surface area are two main directions for the construction and improvement of the performance of porous hydrogen-bonded organic frameworks (HOFs). Herein, a hexaazatriphenylene (HAT) derivative that possesses six carboxyaryl groups serves as a suitable building block for the systematic construction of thermally and chemically durable HOFs with high surface area through shape-fitted docking between the HAT cores and interpenetrated three-dimensional network. A HAT derivative with carboxybiphenyl groups forms a stable single-crystalline porous HOF that displays protic solvent durability, even in concentrated HCl, heat resistance up to 305 °C, and a high Brunauer–Emmett–Teller surface area [SA_(BET)] of 1288 m² g^?1. A single crystal of this HOF displays anisotropic fluorescence, which suggests that it would be applicable to polarized emitters based on robust functional porous materials.

Full text of DOI:10.1002/anie.201805472

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Accepted Article
Title: Docking Strategy to Construct Thermostable, Single-crystalline,
Hydrogen-bonded Organic Framework with Large Surface Area
Authors: Ichiro Hisaki, Yuto Suzuki, Eduardo Gomez, Boiko Cohen,
Norimitsu Tohnai, and Abderrazzak Douhal
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201805472
Angew. Chem. 10.1002/ange.201805472
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10.1002/anie.201805472
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Docking Strategy to Construct Thermostable, Single-crystalline,
Hydrogen-bonded Organic Framework with Large Surface Area
Ichiro Hisaki,*[a] Yuto Suzuki,[a] Eduardo Gomez,[b] Boiko Cohen,[b] Norimitsu Tohnai,[a] and
Abderrazzak Douhal*[b]
Abstract: Enhancement of thermal and chemical durability and an
increase of surface area are two main directions for the construction
and improvement of the performance of porous hydrogen-bonded
organic frameworks (HOFs). Herein, we propose that
a
hexaazatriphenylene (HAT) derivative, which possesses six
carboxyaryl groups, is a suitable building block for the systematic
construction of thermally and chemically durable HOFs with large
surface area due to shape-fitted docking between the HAT cores
and interpenetrated three-dimensional network. We demonstrate
that a HAT derivative with carboxybiphenyl groups (CBPHAT) forms
a stable single-crystalline porous HOF (CBPHAT-1a) that possesses
protic solvent durability, even for concentrated HCl, heat resistance
up to 305 °C, and a high Brunauer-Emmett-Teller surface area
[SA(BET)] of 1288 m2 g−1. A single crystal of CBPHAT-1a has
anisotropic fluorescence, which suggests that it would be applicable
to polarized emitters based on robust functional porous materials.
Porous organic frameworks have attracted much attention in the
fields of materials chemistry and crystal engineering.[1] Both the
structural and electronic versatility of organic molecules enable
the functionality of these frameworks to be tuned for applicability
as selective gas storage/separation materials, catalysts,
chemical sensors, molecular rotors and optoelectronic
materials.[2] Covalent organic frameworks (COFs) are widely
investigated for such applications due to their shape-persistent
rigid frameworks connected through covalent bonds and high
designablility from structural and electronic aspects.[3,4] However,
the crystallinity of many COF systems is insufficient,[5,6] which
prevents precise discussion of the structure-property
relationships.[7]
Hydrogen-bonded organic frameworks (HOFs), on the other
hand, are available as highly crystalline materials (single crystals
in many cases) via a simple recrystallization process because
reversible H-bonding allows self-repair of irregular molecular
connections, which enables precise structural elucidation by
single-crystal X-ray diffraction (SXRD) analysis.[8] However, such
reversibility and the weakness of H-bonds frequently cause the
collapse of the frameworks after desolvation, so there is a lack
of a universalistic design strategy for HOFs. To resolve these
problems, well-designed supramolecular synthons[9] have been
applied,[10] such as benzimidasolone,[10h] pyrazole,[10j,q] the 2,4-
Figure 1. (a) HAT derivatives with carboxyaryl groups (b) Hierarchical
interpretation of a stable rigid HOF (CPHAT-1a) through (1) three-dimensional
(3D) networking of CPHAT via helical H-bonding, (2) network interpenetration,
and (3) shape-fitted docking of twisted HAT cores.
diaminotriazinyl group,[11] as well as a dimer of carboxy groups
which is the most classic and simplest supramolecular
synthon.[12,13]
However, it remains a challenge to obtain sophisticated
HOFs with precise crystal structures, large permanent pores,
and both chemical and thermal stability. Only a handful of HOFs
have been reported with both upper temperature limits of over
200 °C and Brunauer-Emmett-Teller (BET) surface areas
[SA(BET)] of over 1000 m2 g−1; these are HOF-TCBP reported by
Wu and Yuan et al.,[12g] trispyrazole derivatives by Miljanić et
al.,[10j,q] IISERP-HOF1 reported by Vaidhyanathan et al.,[12e] and
HOF-5a reported by Chen et al.[11c] A more generalized strategy
is required to achieve such HOFs systematically.
In connection with this, we previously revealed that
hexaazatriphenylene
(HAT)
possessing
peripheral
carboxyphenyl groups (CPHAT-1) gave a rigid HOF (CPHAT-
1a), which achieves a single-crystalline porous structure with
significant heat resistance up to 339 °C and SA(BET) of 649 m2
g−1.[14] As shown in Figure 1, a rigid HOF CPHAT-1a is formed
through (1) formation of a three-dimensional (3D) network
connected by
a
H-bonded infinite helical motif, (2)
[a]
[b]
Dr. I. Hisaki, Y. Suzuki, Dr. N. Tohnai
interpenetration of the network, and (3) shape-fitted docking of
HAT cores, which seem to be important structural factors to
construct highly-stable HOFs with large pores.
Herein, we would like to propose that HAT derivatives
possessing peripheral carboxyaryl groups could be a platform to
construct highly-stable HOFs with large pores. As a proof of the
concept, we demonstrate that an expanded HAT derivative with
Department of Material and Life Science, Graduate School of
Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-
0871 (Japan)
E-mail: hisaki@mls.eng.osaka-u.ac.jp
E. Gomez, Dr. B. Cohen, Prof. Dr. A. Douhal
Departamento de Quimica Fisica, Facultad de Ciencias Ambientales
y Bioquimica, and INAMOL, Universidad de Castilla-La Mancha,
Avenida Carlos III, S/N, 45071 Toledo (Spain)
E-mail: Abderrazzak.Douhal@uclm.es
carboxybiphenyl groups (CBPHAT) gives
a
stable has
Supporting information for this article is given via a link at the end of
the document.
possessing protic solvent durability, even for conc. HCl, heat
resistance up to 305 °C, and a high SA(BET) of 1288 m2 g−1.
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Scheme 1. Synthesis of CBPHAT
Hexaaminobenzene (2), which was synthesized by
reduction of 1,3,5-triamino-2,4,6-trinitrobenzene (1),[15] was triply
condensed with bis(biphenyl)dione derivative 3 under acidic
conditions to afford HAT derivative 4 in 37% yield in two steps
from 1. Hydrolysis of 4 gave CBPHAT in 95% yield. The
synthesized CBPHAT was then crystallized by slow evaporation
from a solution of N,N-dimethylformamide (DMF) and 1,2,4-
trichlorobenzene (TCB) at 60 °C to give a pale yellow needle
crystalline precipitate denoted as CBPHAT-1(TCB).[16]
The crystal structure of CBPHAT-1(TCB) is shown in Figure
2a, in which CBPHAT molecules crystallize into the P-3 space
group to form a porous hexagonal framework. The carboxy
groups form self-complementary H-bonds to give helical strands
(Figure 2b). The O1···O3 and O2···O4 distances of the H-bonds
are 2.62 and 2.57 Å, respectively. The crystal structure of
CBPHAT-1(TCB) is isostructural with that of previously reported
CPHAT-1(TCB) (Figure 2c). CBPHAT molecules are one-
dimensionally stacked along the b axis with a staggered angle of
60° and intermolecular distances of 3.56 Å (Figure 2d). The
CBPHAT molecule has a twisted conformation due to packing
forces; the root mean square deviation (RMSD) of the HAT core
is 0.204 Å, which enables shape-fitted docking between
adjacent HAT cores. This twisted conformation also makes six
peripheral carboxybiphenyl groups alternately directed up and
down (torsion angle between the adjacent biphenyl groups is
22.1°), which results in the construction of a 3D H-bonded
network with primitive cubic (pcu)-topology (Figure 2e). The
network is six-fold interpenetrated to give a significantly rigid
framework. Three-fold helical channels run along the b axis and
the channels have a triangular shaped cross section with a width
of ca. 14.5 Å; the solvent accessible volume was calculated
using the PLATON software[17] to be 45% (Figure 2f). The
channels accommodate TCB molecules, three of which are
located in each edge of a triangular channel with disorder into
two positions (Figure S1), and the others are located in the
center of the channel and are completely disordered.
Figure 2. Crystal structure of CBPHAT-1-(TCB). Packing diagram of (a)
CBPHAT-1 and (c) CPHAT-1(TCB) for reference (CSD Ref Code: MEBKEM).
Solvent molecules accommodated in the channel are omitted for clarity. (b) H-
bonded three-fold helical strand. Symmetry code: (A) –x+y, 1–x, 1+z; (B) 1–y,
1+x–y, 2+z; (C) 1–y, 1+x–y, –1+z. (d) (top) Twisted non-planar conformation of
CBPHAT, where the central HAT moiety is colored green, and (bottom) its
shape-fitted 1D-stacked column. (e) Schematic models of (top) single and
(bottom) six-fold interpenetrated frameworks with pcu topology. (f)
Visualization of the helical channel surface.
S2). To obtain structural information during desolvation by
heating, variable temperature-powder X-ray diffraction (VT-
PXRD) patterns of bulk crystalline CBPHAT-1(TCB) were
recorded while heating from room temperature to 360 °C (Figure
3b). The diffraction intensity of the 100 peak was also plotted
(Figure 3c). As observed in other previously reported
systems,[13c,14] the peak intensity was poor in the low
temperature region (r.t. to 100 °C) because of disordered TCB
molecules inside the channels. Disordered TCB molecules were
removed by heating, so that the peak intensity increased and
reached a plateau at 126 °C. It is noteworthy that the observed
PXRD pattern, which is in good agreement with that of
CBPHAT-1(TCB), was retained up to 305 °C, which indicates
that the framework shows no structural changes upon
desolvation, and that it has significantly high temperature
resistance.
Thermogravimetric (TG) analysis was conducted to examine
the thermal properties (Figure 3a). The TG curve of crystalline
bulk of CBPHAT-1(TCB) reached a plateau at 180 °C via multi-
stepped 53% weight loss and maintained the plateau until the
compound began to decompose at around 320 °C. The
observed weight loss indicates a host/guest ratio of 1/7, which is
also supported by 1H NMR spectroscopy measurements (Figure
Activation of CBPHAT-1(TCB) was accomplished at 150 °C
under vacuum condition for 24 h to yield the activated crystalline
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Figure 4. (a) Gas sorption isotherms of CBPHAT-1a: O2 (77 K), N2 (77 K),
CO2 (195 K), H2 (77 K). Filled symbols: absorption process, open symbols:
desorption process. (b) Pore size distribution calculated by the NLDFT method.
Table 1. Comparison of CPHAT-1a and CBPHAT-1a
CPHAT-1a
pcu
CBAHAT-1a
Network topology
pcu
6
Number of interpenetrated networks
Pore size / Å
4
6.4
14.5
45%
305
1288
Figure 3. Thermal and chemical durability of crystalline CBPHAT-1a. (a) TG
profiles of CBPHAT-1-(TCB) (blue line) and CBPHAT-1a (red line). (b) VT-
PXRD patterns of CBPHAT-1-(TCB) heated from r.t. to 360 °C. (c) Changes of
the 100 peak intensity with temperature. The intensity rapidly decreased at
305–317 °C, which indicated collapse of the framework. (d) POM micrographs
of CBPHAT-1a under ambient light (top) and UV light with a wavelength of
365 nm. (d) PXRD patterns of CBPHAT-1a simulated from SXRD data,
before soaking, and after soaking in hot solvents for 7 days: CHCl3 (60 °C),
toluene (100 °C), ethanol (60 °C), water (100 °C), and, 37% HCl (60 °C).
Void ratio[a]
31%
339
Upper temperature limit / °C
SA(BET) / m2g-1
649[a]
[a] The value was estimated by PLATON software[17]
.
with O2 and N2, the isotherm for CO2 increased relatively gently
in the low pressure region (<7 kPa).
material CBPHAT-1a. Complete desolvation was confirmed by
TG analysis (Figure 3a) and H NMR spectroscopy (Figure S3).
1
A comparison of the structural parameters of CBPHAT-1a
and the previously reported CPHAT-1a is given in Table 1. As
expected, CBPHAT-1a has a similar molecular conformation,
hydrogen-bonded framework, 1D stacking columns, and
hexagonal arrangements of the columns, while the number of
intercalated frameworks is different due to the length of the arms
(four-fold for CPHAT-1a and six-fold for CBPHAT-1a). By
expansion of the aryl arm, the width of pore, the void ratio and
SA(BET) are increased from 6.4 Å, 31%, and 649 m2 g-1 to 14.5 Å,
45%, and 1288 m2 g-1, respectively. The formation of
isostructural porous frameworks is quite rare for HOF
systems,[19] which indicates that the present HAT system can be
used as a platform to construct isostructural HOFs with different
void sizes.
CBPHAT-1a retained single crystallinity, as indicated by
polarized optical microscopy (POM) observation (Figure 3d), and
SXRD analysis of CBPHAT-1a was successfully accomplished.
CBPHAT-1a has the same framework as CBPHAT-1(TCB)
(Table S1), although a very slight increase of the a, b and c axes
was observed. The framework of CBPHAT-1a resisted protic
solvents, which would typically cleave the H-bonds.[18] PXRD
patterns of CBPHAT-1a shown in Figure 3e retain the original
profile after soaking in chloroform at 60 °C, toluene at 100 °C,
ethanol at 60 °C, water at 100 °C, and 37% HCl at 60 °C for 7
days. However, alkaline aqueous solution, such as KOH,
immediately dissolved the crystalline powder of CBPHAT-1a,
which is the durability limitation of HOFs connected by the
dimerization of carboxy groups.
The bulk of CBPHAT-1a and its butyl ester derivative (4)
show a broad absorption band between 300 and 500 nm, and a
green-yellow emission with intensity maxima around 500 nm
(Figures S5 and S6). The fluorescence quantum yield of the
HOF is 5.7%. Fluorescence confocal microscopy measurements
on CBPHAT-1a single crystals showed highly anisotropic
emission behavior (Figures 5a and b). The anisotropy histogram
for the crystals oriented perpendicularly to the plane of
observation has a value of 0.45, while those rotated by 90°
(parallel orientation) give a value of –0.30. Similar anisotropy
The permanent porosity of CBPHAT-1a was evaluated from
N2, O2, CO2, and H2 gas sorption experiments at 77, 195, 77,
and 77 K, respectively (Figure 4a). CBPHAT-1a has a type-I N2
sorption isotherm with an uptake of 362 cm3 g-1 at 101 kPa. The
SA(BET) and pore size calculated using non-local density
functional theory (NLDFT) for the N2 isotherm were 1288 m2 g-1
and 1.2 nm, respectively (Figures 4b and 4S). Uptakes of other
gases were 427 cm3 g-1 for O2 at 20 kPa, 305 cm3 g-1 for CO2 at
100 kPa, and 111 cm3 g-1 (1 wt%) for H2 at 102 kPa. Compared
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derivative with carboxybiphenyl groups (CBPHAT) yields a
significantly stable single-crystalline porous HOF (CPBHAT-1a)
with protic solvent durability, even for conc. HCl, heat resistance
up to 305 °C, and a high SA(BET) of 1288 m2 g−1. To explore
HOFs with larger pores and more stability, HAT derivatives with
various longer aryl groups are under investigation in our
laboratory.
Acknowledgements
This work was supported by Grant-in-Aid for Scientific Research
Projects from Japan (KAKENHI; JPT15K04591 and
JPTA18H019660), and from Spain (MINECO; MAT2014-57646-
P). Prelimilaly crystal structure analysis was conducted using
the BL38B1 at SPring-8 with approval of the Japan Synchrotron
Radiation Research Institute (JASRI) (Proposal Nos. 2017A1211
and 2017B1322). E.G. thanks the MINECO for the PhD
fellowship: FPU15/01362.
Figure 5. Fluorescence properties of CBPHAT-1a single crystals. a) and b)
Histograms of the emission anisotropy for 2 positions of CBPHAT-1a crystal.
The insets show images of the crystals. c) Emission spectra at different points
of a CBPHAT-1a crystal. The inset shows an image of the crystal and the
points of measurement. d) Fluorescence decay of a CBPHAT-1a crystal; the I
and II decays were measured using FF01-470_28-25 and HQ550LP filters
(Chroma).
Keywords: porous organic framework • hydrogen bond •
carboxylic acid • fluorescence • crystal engineering
References and Notes
behavior has been reported for CPHAT-1a.[14] This strong
dependence of the anisotropy on the crystal orientation indicates
an ordered crystalline structure for CBPHAT-1a with preferential
orientation of the molecular dipole moments perpendicular to the
long crystal axis with the π-π columnar stacking direction
parallel to the length axis of the crystal. The emission spectra of
CBPHAT-1a do much not vary between the different crystals,
although they do change depending on the position within each
crystal. At the center, the spectra have emission intensity
maxima at ca. 475 nm (Figure 5c), while those collected close to
the edges shift to redder wavelengths (ca. 510 nm) and become
broader. This behavior is explained in terms of the presence of
structural defects along the edges of the crystals. The emission
decays of CBPHAT-1a single crystals collected in the blue
(450–500 nm) and green/red (550–660 nm) region of the
spectrum give lifetimes of 1 ~ 0.4 ns (94%) and 2 ~ 1.2 ns (6%),
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carboxyphenyl groups in CBPHAT-1a. Thus, the expansion of
the aryl arm in CBPHAT-1a and the change in the pore size did
not significantly alter the optical and photophysical properties of
the resultant HOF structure.
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[16] Crystal data for CBPHAT-1(TCB): (C90H54N6O12)∙3(C6H3Cl3), Fw
=
1955.70, a = b = 29.7532(15) Å, c = 7.1146(6) Å, α = β =90°, γ = 120°,
V = 5454.4(6) Å3, T = 93 K, trigonal, space group P-3, Z = 2, 29812
collected, 7251 unique (Rint = 0.097) reflections, the final R1 and wR2
values 0.130 (I > 2.0(I)) and 0.385 (all data), respectively. Crystal
data for CBPHAT-1a: C90H54N6O12, Fw = 1411.45, a = b = 29.7810(10)
Å, c = 7.1709(3) Å, α = β =90°, γ = 120°, V = 5507.9(3) Å3, T = 93 K,
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trigonal, space group P-3, Z = 2, 16474 collected, 7205 unique (Rint
=
0.075) reflections, the final R1 and wR2 values 0.078 (I > 2.0 (I)) and

0.241 (all data). CCDC1841012 [CBPHAT-1(TCB)] and CCDC1841011
(CBPHAT-1a) contain the supplementary crystallographic data for this
paper. These data are provided free of charge by The Cambridge
Crystallographic Data Centre.
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[18] CBPHAT-1a is figurally soluble in dichloromethane and moderately
soluble in DMF.
[19] Recently isostructural HOFs with large pores is reported, see ref.10q.
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10.1002/anie.201805472
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
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COMMUNICATION
We demonstrated that HAT
I. Hisaki,* Y. Suzuki, E. Gomez, B.
derivatives are a suitable building
block for the systematic construction
of stable hydrogen-bonded
Cohen, N. Tohnai, A. Douhal*
Page No. – Page No.
framework, and that the derivative
with carboxybiphenyl groups forms a
stable single-crystalline porous
framework (CBPHAT-1a) that
possesses protic solvent durability,
heat resistance up to 305 °C, and
SA(BET) of 1288 m2 g−1.
Docking Strategy to Construct
Thermostable, Single-crystalline,
Hydrogen-bonded Organic
Framework with Large Surface Area
This article is protected by copyright. All rights reserved.