Non-Interpenetrated Single-Crystal Covalent Organic Frameworks

Article abstract of DOI:10.1002/anie.202007230

Growth of covalent organic frameworks (COFs) as single crystals is extremely challenging. Inaccessibility of open-structured single-crystal COFs prevents the exploration of structure-oriented applications. Herein we report for the first time a non-interpenetrated single-crystal COF, LZU-306, which possesses the open structure constructed exclusively via covalent assembly. With a high void volume of 80 %, LZU-306 was applied to investigate the intrinsic dynamics of reticulated tetraphenylethylene (TPE) as the individual aggregation-induced-emission moiety. Solid-state ²H NMR investigation has determined that the rotation of benzene rings in TPE, being the freest among the reported cases, is as fast as 1.0×10⁴ Hz at 203 K to 1.5×10⁷ Hz at 293 K. This research not only explores a new paradigm for single-crystal growth of open frameworks, but also provides a unique matrix-isolation platform to reticulate functional moieties into a well-defined and isolated state.

Full text of DOI:10.1002/anie.202007230

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Non-Interpenetrated Single-Crystal Covalent Organic
Frameworks
Authors: Lin Liang, Yi Qiu, Wei David Wang, Jing Han, Yi Luo, Wei Yu,
Guan-Lin Yin, Zhi-Peng Wang, Lei Zhang, Jianwei Ni, Jing
Niu, Junliang Sun, Tianqiong Ma, and Wei Wang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202007230
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10.1002/anie.202007230
Angewandte Chemie International Edition
RESEARCH ARTICLE
Non-Interpenetrated Single-Crystal Covalent Organic Frameworks
Lin Liang+, Yi Qiu+, Wei David Wang, Jing Han, Yi Luo, Wei Yu, Guan-Lin Yin, Zhi-Peng Wang, Lei
Zhang, Jianwei Ni, Jing Niu, Junliang Sun,* Tianqiong Ma,* Wei Wang*
[*]
L. Liang,[+] Dr. W. D. Wang, J, Han, Prof. Dr. W. Yu, G.-L. Yin, Z. -P. Wang, J. Ni, J. Niu, Dr. T. Ma, Prof. Dr. W. Wang
State Key Laboratory of Applied Organic Chemistry
College of Chemistry and Chemical Engineering
Lanzhou University, Lanzhou, Gansu 730000 (China)
E-mail: wang_wei@lzu.edu.cn
Y. Qiu,[+] L. Zhang, Prof. Dr. J. Sun, Dr. T. Ma
College of Chemistry and Molecular Engineering
Beijing National Laboratory for Molecular Sciences
Peking University, Beijing 100871 (China)
E-mail: junliang.sun@pku.edu.cn, tianqiongma@pku.edu.cn
Dr. Y. Luo
Department of Materials and Environmental Chemistry
Stockholm University, 10691 Stockholm (Sweden)
These authors contributed equally to this work.
[+]
Supporting information for this article is given via a link at the end of the document.
Abstract: Growth of covalent organic frameworks (COFs) as single
crystals is extremely challenging. Inaccessibility of open-structured
single-crystal COFs prevents the exploration of structure-oriented
applications. Herein we report for the first time a non-interpenetrated
single-crystal COF, LZU-306, which possesses the open structure
constructed exclusively via covalent assembly. With a high void
volume of 80%, LZU-306 was applied to investigate the intrinsic
dynamics of reticulated tetraphenylethylene (TPE) as the individual
aggregation-induced-emission moiety. Solid-state 2H NMR
investigation has determined that the rotation of benzene rings in
TPE, being the freest among the reported cases, is as fast as 1.0 ×
104 Hz at 203 K to 1.5 × 107 Hz at 293 K. This research not only
explores
a new paradigm for single-crystal growth of open
frameworks, but also provides a unique matrix-isolation platform to
reticulate functional moieties into a well-defined and isolated state.
Introduction
Covalent assembly of organic molecules into extended
single crystals is a long-standing challenge.[1-4] The bottleneck
lies in the contradiction between the critical demand for error-
checking in crystallization and the intrinsic lack of reversibility in
covalent bonding. This severe limitation in three-dimensional
(3D) assembly has not been broken through until very recently.
Wuest succeeded in linking tetranitroso monomers via weak
azodioxy bonds into nonporous single-crystal polymers.[4a] We
developed a modulation strategy to construct, for the first time,
single-crystal covalent organic frameworks (scCOFs) with
Figure 1. (a) Covalent assembly of TPE-NH2 and ADA-CHO into single-crystal
LZU-306 via the modulation strategy; (b) Non-interpenetrated pts topology; (c)
Crystal structure of LZU-306. TPE moieties: blue; ADA moieties: gray;
hydrogen atoms were omitted for clarity.
adamantane (ADA)[6f,9] based tetrahedral node (Figure 1).
Applying the modulation strategy developed by us,[4b] we were
able to grow LZU-306 as tunable-sized single crystals. Structural
analysis concluded that it possesses a non-interpenetrated open
framework with a pts[6g] topology. Unlike previously reported
scCOFs,[4b] LZU-306 is structurally featured in the entire
connection via covalent bonding, in which the TPE moieties
have been spatially and evenly separated by the rigid ADA
spacers. Accordingly, it provides a matrix-isolation platform to
investigate the intrinsic dynamics of individual TPE moiety and
the ultrafast rotation of phenyl rings has been verified by solid-
permanent
porosity.[4b]
Nevertheless,
densely-packed
interpenetrated networks are exclusively formed[4] with the
ubiquitous existence of non-covalent interactions (such as -
stacking) between the adjacent nets. This interpenetration will
hinder the structure-oriented applications, especially when the
availability of abundant void spaces[5] becomes the key factor.
Therefore, further advance to grow non-interpenetrated scCOFs
as open frameworks is in urgent need.
Herein, we report the first non-interpenetrated scCOF,
named LZU-306, which is covalently assembled[6] from a
tetraphenylethylene (TPE)[7,8] based quadrilateral linker, and an
1
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10.1002/anie.202007230
Angewandte Chemie International Edition
RESEARCH ARTICLE
2
state H NMR spectroscopy. We expect that this research will
activated sample with the unit cell of a = 23.45 Å, b = 20.75 Å, c
= 23.85 Å, α = γ = 90°, and β = 91.56° in the C2 space group. As
shown in Figure 3c, the calculated PXRD pattern of the non-
interpenetrated structure agrees well with the experimental
pattern of the activated LZU-306.
pave the way for the covalent growth of open-structured single
crystals, based on which many new applications may become
feasible.
Results and Discussion
With aniline as the modulator,[4b] we previously succeeded in
synthesizing dia- and lon-topological 3D scCOFs. However, the
use of methane-based tetrahedral monomers has inevitably
resulted in the formation of densely-packed interpenetrated
scCOFs. We therefore selected bulkier ADA-based nodes
together with a propeller-like TPE linker so as to grow scCOFs
with new topology and less interpenetration. Adamantane-
1,3,5,7-tetracarbaldehyde (denoted as ADA-CHO) was
eventually employed because it has much better solubility than
its amine analogue. Indeed, the modulation strategy is well
applicable to grow pts-topological LZU-306 as tunable-sized
scCOFs from ADA-CHO and tetrakis(4-aminophenyl)ethylene
(denoted as TPE-NH2) (Figure 1a). The synthetic details have
been described in the Supporting Information. Optical
microscopy and scanning electron microscopy (SEM) images
revealed that all the samples possessed uniform octahedral
morphology (Figure 2). For example, under the synthetic
condition without aniline [120 °C , 5 days, in 1,4-dioxane/6M
HOAc (10/1)], 200 nm-sized crystals were obtained (Figure 2a).
While by adding aniline (50 equiv.) [30 °C , 25 days in 1,4-
dioxane/15M HOAc (7.5/1)], yellow-colored single crystals could
be harvested with the size of 50 μm (Figures 2e and 2f).
Figure 3. (a) Reciprocal planes of SXRD data from a 50 μm-sized solvent-
exchanged single crystal. (b) Reconstructed 3D RED data of a 500 nm-sized
activated single crystal. (c) Experimental (red) and calculated (black) PXRD
patterns of the activated LZU-306. The positions of Bragg reflections under the
patterns are shown in blue.
Further characterization confirmed the highly-ordered and
non-interpenetrated structure. Solid-state 13C cross-polarization
magic-angle spinning (CP/MAS) NMR measurement gave sharp
peaks with the full width at half maximum (FWHM) narrow to 125
Hz: the carbon atoms can be resolved with the resolution down
to 1 ppm (Figure 4a). The absence of characteristic signals of
the terminal –CHO groups (at ca. 205 ppm in the 13C CP/MAS
NMR spectrum in Figure S3 and at ca. 1717 cm-1 in the FT-IR
spectrum in Figure S5) indicates the completeness of covalent
linking in LZU-306. Nitrogen adsorption-desorption isotherms
showed a reversible type-I isotherm (Figure 4b); the Brunauer-
Emmett-Teller (BET) and Langmuir surface areas were
determined as large as 2059 and 2402 m2 g-1, respectively
(Figures S6 and S7). The average pore width of ~10.9 Å with a
narrow pore-size-distribution (Figure 4b inset) matches well with
the theoretical value of 11.0 Å. 129Xe atoms adsorbed in LZU-
306 showed only one signal (δ = 121 ppm) with a narrow FWHM
of 671 Hz in the 129Xe NMR spectrum (Figure 4c), further
verifying the formation of uniform pores. In addition, the
thermogravimetric analysis (TGA) demonstrated that LZU-306 is
stable up to 530 °C under nitrogen atmosphere (Figure S12).
As shown in Figure 1c, the fragments in LZU-306 are loosely
packed into a highly open framework that possesses a large
void volume of 80%[10] and a low density of 0.33 g cm-3. Note
that, more densely packed structures with 2- or 3-fold
interpenetration would lead to a lower void volume of 56% or
Figure 2. (a to e): SEM images of single-crystal LZU-306 with the average
sizes of ~200 nm, 1 μm, 5 μm, 20 μm, and 50 μm, obtained in the presence of
aniline with the amount of 0, 10.0, 12.5, 40.0, and 50.0 equiv., respectively. (f)
The optical microscopy image of 50 μm-sized LZU-306.
Structural analysis disclosed that LZU-306 possesses a non-
interpenetrated pts structure, as shown in Figure 1. SXRD
measurement with synchrotron light sources on a 50 μm-sized
solvent-exchanged sample (Figure 3a) indicates an original
tetragonal unit cell with a = b = 15.32 Å, c = 24.89 Å. Rotation
electron diffraction (RED) on a 500 nm-sized activated sample
(Figure 3b) gives a similar unit cell with a = b = 15.72 Å, c =
24.05 Å. Based on the diffraction data, a non-interpenetrated pts
framework could be established in the tetragonal symmetry. By
combining the powder X-ray diffraction (PXRD) data, the
structure was rationally converted into a C-centered monoclinic
lattice with a slight incline of β (Figure S15-S18). Le Bail fitting of
PXRD data (Figure S16) further confirmed the structure of the
30%, and,
respectively.[10] In reported scCOFs, the dense packing in the
a higher density of 0.66 or 1.00 g
cm-3,
…
interpenetrated dia or lon topology renders the   distance
2
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10.1002/anie.202007230
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RESEARCH ARTICLE
between the adjacent nets into the range of 4.6 to 5.1 Å (Table
LZU-306 (k = 1.5 × 107 Hz at 293 K, Figure 5b) is three orders of
magnitude faster than that of TPE-containing MOF (k = 1.0 × 104
at 300 K).[8g] Moreover, as shown in Figures S28 and S29,
Arrhenius plot and density functional based tight binding plus
(DFTB+) method have derived the experimental activation
energy of 40 kJ mol-1 with the pre-exponential factor[15] of k0 =
2.5 × 1014 Hz and the theoretical activation barrier of 32 kJ mol-1,
respectively. Comparison of these values with those for TPE-
containing materials[8g-j] concluded that the benzene rings in
LZU-306 experienced the freest rotation. Therefore, in difference
from the dispersion states in solution or the aggregation states in
solid, a new dispersion state of TPE molecules in single crystals
has been provided herein, based on which the intramolecular
rotation of -flipping could be explicitly analyzed.
S2).[4b] On the contrary, the shortest intermolecular

…

distance in LZU-306 reaches 10.6 Å. As expected, the use of
rigid and bulky ADA spacer did render loosely-packed pts
structures.[9]
Figure 4. Characterization of single-crystal LZU-306. (a) 13C CP/MAS NMR
spectrum. Assignments of 13C chemical shifts were indicated in the chemical
structure. The peak region between 36 to 44 ppm has been magnified in the
inset. Asterisks denote the spinning sidebands. (b) N2 adsorption (filled
symbols) and desorption (empty symbols) isotherms. Inset: pore-size
distribution. (c) 129Xe NMR spectrum of adsorbed xenon atoms in LZU-306.
Figure 5. (a) Covalent isolation of TPE moiety in the framework of LZU-306.
(b) Experimental (black) and simulated (blue) quadrupolar spin-echo solid-
state 2H NMR spectra of activated d-LZU-306 recorded at 203 to 293 K. (c) -
flipping around the C2 symmetry axis of benzene rings in d16-TPE moiety.
Accurate isolation of molecules into an individual state,
especially in a single-crystal state, helps to study the single-
molecule
behavior,
such
as
dynamics,
magnetism,
luminescence, or single-site catalysis.[11] For example, in order
to reveal the mechanism of intramolecular rotation in AIE
systems,[12] elimination of intermolecular interactions by efficient
isolation of AIE moieties is crucial.[13] In this context, the
archetypal AIE moiety, TPE,[7] has been precisely reticulated
and remotely separated from each other in LZU-306. This new
model allowed us to further investigate the intrinsic dynamics of
AIE moieties without the disturbance of intermolecular
interactions (Figure 5).
To quantitatively evaluate the rotational dynamics of TPE,
we performed variable-temperature solid-state 2H NMR
experiments[14] on a selectively deuterated LZU-306 sample
(denoted as d-LZU-306 in which the hydrogen atoms of TPE
moieties were deuterium-substituted; the synthetic detail and
structural characterization have been shown in Supporting
Information). In the spectra recorded at temperatures from 203
to 293 K (Figure 5b), the line shapes showed progressive
variation from a typical Pake pattern (Q = 129 kHz) to a small-
splitting pattern (Q/4 = 31 kHz). The line shapes indicate that the
fast flipping of phenyl rings occurs even at 293 K. The spectra
were further simulated to derive the rotational frequency (k) of
benzene-rings around the C2 symmetry axis (Figure 5c). The
results indicate that the rotation frequency of benzene rings in
Conclusion
In conclusion, we have accomplished the preparation of the
first single-crystal organic framework that is exclusively
connected via covalent bonding. Constructed with the rigid and
bulky adamantane-based node by using the aniline-based
modulation strategy, the pts-topological LZU-306 possesses a
highly-open structure with the void volume of 80%. This unique
structure provides a matrix-isolation platform to further study the
single-molecule behavior in the absence of non-covalent
interactions. As an example, the intrinsic rotation dynamics of
the TPE moiety has been assessed via variable-temperature
solid-state 2H NMR spectroscopy. This approach thus explores a
new protocol to covalently assemble organic molecules into
extended single crystals for structure-property-relationship
investigations.
Acknowledgements
We acknowledge the financial support from the National Natural
Science Foundation of China (Nos. 21632004, 21871009,
3
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10.1002/anie.202007230
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RESEARCH ARTICLE
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We thank the staff of beamlines BL17B/BL17U at Shanghai
Synchrotron Radiation Facility for assisting with the SXRD data
collection.
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Keywords: 3D COF • single-crystal • non-interpenetrated •
matrix-isolation • solid-state NMR
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10.1002/anie.202007230
Angewandte Chemie International Edition
RESEARCH ARTICLE
Entry for the Table of Contents
A 3D single-crystal COF with a non-interpenetrated structure was constructed for the first time. The highly open framework provides a
unique matrix-isolation platform to investigate the intrinsic dynamics of individual AIE moiety.
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