A Dynamic Three-Dimensional Covalent Organic Framework

Article abstract of DOI:10.1021/jacs.7b01097

A guest-induced reversible crystal-structure transformation is identified in a new 3D covalent organic framework (COF) by comprehensive analyses using powder X-ray diffraction, organic vapor sorption isotherm, and ¹²⁹Xe NMR spectroscopy. The revolving imine bond in interpenetrating 3D networks is uncovered as the key to the dynamic behavior, the potential applications of which are illustrated by gas separation and heterogeneous catalysis, thus paving the way to the design of stimuli-responsive and multifunctional COF materials.

Full text of DOI:10.1021/jacs.7b01097

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Communication
A Dynamic Three-Dimensional Covalent Organic Framework
Yun-Xiang Ma, Zhi-Jun Li, Lei Wei, San-Yuan Ding, Yue-Biao Zhang, and Wei Wang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b01097 • Publication Date (Web): 28 Mar 2017
Downloaded from http://pubs.acs.org on March 28, 2017
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A Dynamic Three-Dimensional Covalent Organic Framework
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Yun-Xiang Ma,†,# Zhi-Jun Li,†,# Lei Wei,‡ San-Yuan Ding,† Yue-Biao Zhang,*,‡,□ and Wei Wang*,†,§
†State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou,
Gansu 730000, China
‡School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
§Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300071, China
□Joint Laboratory of Low-Carbon Energy Science, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai
201203, China.
Supporting Information Placeholder
ABSTRACT: A guest-induced reversible crystal-structure transfor-
mation is identified in a new 3D covalent organic framework (COF) by
the comprehensive analyses of powder X-ray diffraction, organic vapor
sorption isotherm, and 129Xe NMR spectroscopy. The utilization of
revolving imine-bond in interpenetrating 3D networks is uncovered as
the key to the dynamic behavior, whose potential applications have
been illustrated by gas separation and heterogeneity catalysis, thus,
paving the way to the design of stimuli-responsive and multifunctional
COF materials.
Dynamic behavior, as evidenced by crystal structure transformation,
Figure 1. (a) Solvothermal synthesis of a three-dimensional (3D)
COF material, LZU-301, via imine condensation. For clarity, only the
single framework of LZU-301 is shown. (b) Side and top views of po-
rous crystalline structure of LZU-301, which features with a 9-fold
interpenetration of the underlying diamond net.
can be induced in crystalline porous materials by guest molecules,
pressure, and temperature. This highly desired property is most often
exemplified by metal–organic frameworks (MOFs)1 in order to achieve
stimuli-driven responses for sensing, selective adsorption and separa-
tion, gas storage, and heterogeneous catalysis.2,3 More robust crystal-
line porous materials, termed covalent organic frameworks (COFs),4
have emerged as the new frontier for materials, in which the notion that
“chemistry of the framework” has been achieved by extending Lewis’
concept of “the atom the molecule” to precisely control and manipulate
the structure and function of matter.5 Great efforts have been devoted
to the crystallization and structural determination of COFs, construct-
ed solely by organic building blocks linked entirely through strong
covalent bonds into 2D and 3D networks.6 With a higher degree of
flexibility of the constituents, there have been some hints for dynamic
behavior in COFs,7,8 however, principle for the design of dynamic
COFs remains largely untapped. Thus, structural elucidation and fun-
damental understandings are solely needed to propel the exploitation
of COFs as stimuli-responsive materials.
Herein, we report the synthesis and characterization of a new 3D
COF, termed LZU-301 (LZU = Lanzhou University), synthesized via
the imine condensation of (3,3'-bipyridine)-6,6'-dicarbaldehyde
(BPyDA) and tetra-(4-anilyl)methane (TAM) to give pyridyl-
functionalized 1D channels encompassed by the highly interpenetrated
diamond networks (dia-C9-net, Figure 1). Notably, reversible crystal-
transformation and dynamic response of COF have been comprehen-
sively proven by powder X-ray diffraction (PXRD) analysis, organic
vapor sorption isotherms, and 129Xe NMR spectroscopy. We have un-
covered that imine bonds revolving as molecular pedal within inter-
penetrating 3D networks is the key to access such dynamic behavior.
LZU-301 is a proven dynamic adsorbent for the selective capture of
CO2 from both dry and humid gas mixtures, in which a water-assisted
gating CO2 adsorption enhancement was observed. Probed by the well-
studied Knoevenagel condensation, LZU-301 has shown catalytic
activity within pores, capable for the inclusion of large molecules, inter-
action with substrates, and extrusion of products, showing the possibil-
ity for design more advance COF catalysts integrated with dynamic
response in the future.
Details of the synthetic procedure and characterization of LZU-301
are provided in the Supporting Information (SI, section S1). The suc-
cessful formation of the imine linkage was confirmed by both FT-IR
(Figures S1–S2) and 13C solid-state NMR spectroscopy (Figure S3–
S5). The crystallinity and phase purity were validated by PXRD (Fig-
ures S10–S12) and scanning electron microscopy (SEM, Figure S8).
The thermal stability up to 512 °C was indicated by thermogravimetric
analysis (TGA, Figure S9). The permanent porosity, specific surface
area, and pore volume were assessed by the N2 physisorption isotherm
at 77 K (Figures S21–S23), which show that LZU-301 exhibits micro-
porosity with the Brauner-Emmett-Teller (BET) surface area of 654
m2 g-1. These structural details undoubtedly support the formation of
LZU-301 with structural regularity, architectural robustness, and in-
trinsic porosity.
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Figure 2. (a) Indexed PXRD pattern (red) of activated sample and Pawley fitting profile (blue) supporting the contracted structure (right attached)
presents in LZU-301 upon activation. (b) Indexed PXRD pattern of the THF-solvated sample (red) and Pawley fitting profile (blue) supporting the
transformation into expanded structure (right attached) upon guest inclusion in LZU-301. (c) Recovery of PXRD patterns upon solvated and deso-
lated process showing the reversibility of crystal structural transformation. (d) THF vapor adsorption isotherms of LZU-301 and COF-320 at 283 K
showing dynamic response to vapor pressure for LZU-301. (e) Temperature-dependent (decreased from 273 to 193 K, initial pressure ~14.8 bar)
129Xe NMR spectra with signals attributed to xenon adsorbed in contracted phase (red line) and expanded phase (blue line) of LZU-301, respectively.
(f) Breakthrough curves for gas separation of CO2/N2 (v/v = 10:90) under dry and wet conditions (relative humidity, RH = 17% and 83%, respec-
tively) showing the water-induced gating CO2 uptake.
to a = 27.866(6), b = 30.341(7), c = 7.841(2) Å, and V = 6629(4) Å3.
Noted is the fact that an exceptional expansion of unit cell volume after
solvation is observed (up to 35%), which is attributed to the confor-
mation change of the –C=N– (Figure S17) featuring the ‘pedal’ mo-
tion in crystal.10 The 3D nature in LZU-301 leads to the looser inter-
framework packing (7.8–-8.5 Å of translation along the c axis between
sets; 3.4–4.8 Å separation between closest layers in comparison with
2D COFs usually having layer separation of 3.3 Å) enabling the revolv-
ing of imine bonds.
With the dynamic framework having pore size stretchable from 5.8 ×
10.4 Å2 (contracted form) to 9.6 × 10.4 Å2 (expanded form), we were
puzzled with the one-step shape and lower uptake observed in the N2
adsorption isotherm at 77 K with P/P0 = 10-5 ~ 0.993. Thus, we have
recollected the N2 adsorption at 77 K with P/P0 from 10-7 to 0.999,
which have shown a significant hysteresis of desorption branch (Figure
S24), indicating a partially gate opening triggered by the liquid-like N2.
Assessed from the adsorption and desorption branches, the surface
areas of these two status are 654 and 848 m2/g, and pore volumes are
0.3096 and 0.3872 cm3/g, respectively. To further visualize the gate-
opening effect in LZU-301, vapor adsorption isotherms were collected
on both LZU-301 and COF-320 at 283 K (Figure 2d). Significant
stepwise and hysteresis uptake was observed from LZU-301 in contrast
with the knee shape isotherm for COF-320, indicating LZU-301 re-
tains its contracted phase for dynamic response at higher temperatures
but not the case for COF-320. The uptake of the first step reached 81.6
cm3 g-1 at P/P0 = 0.08 with the calculated pore volume 0.295 cm3 g-1
and then it reached 167 cm3 g-1 at P/P0 = 0.8 with the calculated pore
volume 0.605 cm3 g-1 after the second step, corresponding to the theo-
retical value from the structures of activated LZU-301 (0.296 cm3 g-1)
and THF-solvated LZU-301(0.612 cm3 g-1), respectively.
The structural elucidation of LZU-301 was based on the reticular
chemistry of interpenetration of dia-net7 and single crystal structures of
COF-3208. By modeling crystal structures with multiple interpenetra-
tions and various symmetries, one of the candidate models (Table S2,
ꢀ
space group: I42d) with simulated PXRD matched with that of the
activated sample, which was amended from the low-temperature phase
of COF-3208 by replacing the benzene ring into pyridyl group and
optimizing unit cell with energy minimal. Using this model, the Pawley
refinement of the PXRD patterns converged in small differences be-
tween the experimental and the simulated profiles (Figure 2a), result-
ing in unit cell parameters of a = b = 24.032(3) Å, c = 8.484(1) Å, and
V = 4900(2) Å3 (with Rwp = 1.81% and Rp = 1.35%; Figure 2a).
The crystal-structure transformation was first observed when a dis-
crepancy was identified between the experimental PXRD patterns of
activated and solvated samples of LZU-301 immersed in tetrahydrofu-
ran (THF, Figures 2b and S11), which can be recovered after re-
activation (Figures 2c and S11). Similar changes and recoveries of
PXRD patterns were also observed for the activated sample solvated
with ethanol, acetone, and acetonitrile, where the original 200 peaks
split into two peaks and shifts to lower 2 angles upon solvation (Fig-
ures S13–S16). Comparison of the PXRD patterns of activated and
solvated samples demonstrates that a symmetry breaking and lattice
expansion were happening.9 In light of the orthorhombic phase of
COF-3208, a lower-symmetry model (Table S3) with a space group of
Imma adapting the unaltered dia-C9-net interpenetrated along the c-
axis was built, which is coherent with the observed PXRD pattern.
Based on this model, the Pawley refinement provided a perfect fit be-
tween the simulated and experimental PXRD profiles (Rwp = 1.85% and
Rp = 1.28%; Figure 2b). Accordingly, the unit cell parameters increased
2
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By virtue of the high molecular polarizability and environmentally
were observed, due to the oversize products (3b, 12.8 × 8.2 Å2; 3c, 11.4
× 11.5 Å2, respectively). To confirm the inclusion of 1c with size closed
to the expanded channel (9.6 × 10.4 Å2) of LZU-301, secondary size
selectivity17 was observed by mixed the 1a and 3a in the catalytic reac-
tion, where the clogging of 3a reduced the conversion of 1a. Control
experiments for blank, leaching out, homogeneous catalyst, and non-
porous analogue, as well as cycling reaction of LZU-301 were also per-
formed to ensure the reaction is occurred in the channels of LZU-301
(Table 1 and Section S10 in SI).
sensitive NMR signal for xenon guests,11 the 129Xe NMR spectroscopy
was employed to directly probe the dynamic behavior of LZU-301,
which represents the first time this technique has been used for charac-
terizing COF materials.12 The 129Xe signals were monitored by cooling
down from 273 to 193 K a constant amount of xenon gas within a
sealed tube containing LZU-301 (see SI for experimental details). A
gradual switch from high field to low field was observed with interme-
diate states having two split peaks for the 129Xe signals from 243 to 213
K (Figure 2e). Given the kinetic diameter of xenon (4.4 Å), the con-
tracted LZU-301 (aperture diameters = 5.8 × 10.4 Å2) can only ac-
commodate discrete xenon molecules, while the expanded state (aper-
ture diameters = 9.6 × 10.4 Å2) provides more space for xenon mole-
cules to closely compact for stronger XeXe interactions,11b thus result-
ing in 129Xe NMR signals in lower fields. Similar phenomena have been
observed for flexible MOFs.12a A reversible process was further ob-
served by warming up the sample from 193 to 273 K (Figure S19), in
which the 129Xe signals switched gradually from low to high field. Fur-
thermore, pressure dependent 129Xe NMR spectroscopy was also per-
formed at 233 K (Figure S20), in which the gradual switch from high to
low field was also observed with increasing pressure. All of these results
indicate the reversible pore expansion/contraction in the dynamic
LZU-301 as stimuli responses to adsorption/desorption.
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Table 1. Knoevenagel condensation catalytic experiments.a
Isolated yield for different catalysts (%)
Aldehyde Product
PyMAb
94
LZU-301 LZU-101
COF-320
42
72 (99c)
1a
1b
1c
1a+1cd
3a
3b
3c
3a
21
21
5
~18e
22
13
N/A
95
75
N/A
N/A
N/A
N/A
aGeneral conditions: aldehyde (1, 0.5 mmol), malononitrile (2, 1.5
mmol). bReaction time: 4 hours. cProlong the reaction time to 10 hours.
To exploit the pyridyl moieties in the channel as functional groups
for gas separation, CO2 adsorption properties were assessed by both
static adsorption isotherms and dynamic breakthrough curves. Only
physisorption was observed in CO2 adsorption isotherm measured at
273 and 298 K (Figure S27), with uptakes reaching 2.63 and 1.59
mmol g-1 at 1 bar, respectively. These CO2 uptake capacities are higher
than COFs functionalized with hydroxyl groups and comparable to
COFs functionalized with carboxylate or primary alcohol groups.13 In
order to test LZU-301 under practical applications, breakthrough ex-
periments using CO2/N2 gas mixtures s(v/v = 10:90 at 298 K and 1 bar)
under dry or humid conditions were employed14 (Figure 2f). Suffi-
ciently long retention time of 25 min were observed, in which 0.22
mmol g-1 of CO2 was captured under dry conditions, while longer re-
tention times were seen under wet condition [17% relative humidity
(RH)]. For the latter, LZU-301 adsorbed 0.29 mmol g-1 of CO2. Inter-
estingly, the CO2 capture amount was further enhanced to 0.37
mmol/g under 83% RH, which is even higher than the CO2 uptake
(0.35 mmol/g) of the activated framework at 298 K and P/P0 = 0.1,
indicating a gate-open effect with the presence of water.15 Neither de-
composition nor chemical adsorption was suggested as evidenced by
the solid state 13C NMR spectrum of LZU-301 after CO2 sorption
under humid condition (Figure S6).
To illustrate the inclusion of large molecules, access of interior func-
tionalities, and penitential applications of heterogeneous catalysis,
Knoevenagel condensation reactions, previously well-performed by the
rigid imine COFs,16 were tested on the dynamic LZU-301 with the
additional pyridyl groups functioning as Lewis base. To trigger the
channel expansion of activated LZU-301 as catalyst, the catalytic reac-
tions were conducted in acetonitrile with aromatic aldehydes (1) as
size probes and malononitrile (2) as active methylene reagent to make
larger-sized ,-unsaturated products (3). Indeed, catalytic activity of
LZU-301 was observed for benzaldehyde (1a, 6.5 × 8.5 Å2) converted
into benzylidene-malononitrile (3a, 8.0 × 11.3 Å2) with 72% yield in 6
hours outperforming COF-320 (42% yield) and non-porous analogue
LZU-101 (21%, see SI for synthesis), and achieved 99% yield in 10
hours. For larger-sized substrates, 2-naphthaldehyde (1b, 7.2 × 10.3 Å2)
and 9-anthraldehyde (1c, 8.6 × 11.5 Å2), lower activities and yields
Ratio of 0.25 mmol vs. 0.25 mmol. eGC yield.
d
As a summary, we have identified the structural transformation and
dynamic behavior of a new 3D COF comprehensively via PXRD, vapor
adsorption isotherms, and 129Xe NMR spectroscopy. Beyond the wide-
ly used hinge motion of COO–M in breathing MOFs, we disclosed
here the –C=N– can serve as a versatile molecular pedal for the design
of dynamic COFs. LZU-301 is a proven dynamic adsorbent for the
selective capture of CO2 from both dry and humid gas mixtures, where
a water-assisted gating effect for CO2 capture has been observed for the
first time in COF materials.
ASSOCIATED CONTENT
Supporting Information
13
Detailed synthetic procedures, FT-IR spectra, solid-state C CP/MAS
NMR spectra, SEM images, PXRD patterns, TGA trace, structure
modeling and atom coordinates, gas/vapor sorption isotherms, 129Xe
NMR spectra, and catalytic experiments. These materials are available
free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*zhangyb@shanghaitech.edu.cn;
*wang_wei@lzu.edu.cn
Author Contributions
#These authors contributed equally to this work.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENTS
This work was financially supported by the National Natural Science
Foundation of China (No. 21425206 and 21522105). Y.-B.Z.
acknowledges the support of the 1000 Young Talent Plan. The authors
3
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thank Dr. P.-Q. Liao and Prof. J.-P. Zhang (Sun Yat-Sen University) for
beneficial discussion.
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REFERENCES
(1) (a) Horike, S.; Shimomura, S.; Kitagawa, S. Nat. Chem. 2009, 1, 695. (b)
Férey, G.; Serre, C. Chem. Soc. Rev. 2009, 38, 1380. (c) Schneemann, A.;
Bon, V.; Schwedler, I.; Senkovska, I.; Kaskel, S.; Fischer, R. A. Chem. Soc.
Rev. 2014, 43, 6062. (d) Zhang, J.-P.; Liao, P.-Q.; Zhou, H.-L.; Lin, R.-B.;
Chen, X.-M. Chem. Soc. Rev. 2014, 43, 5789.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(2) (a) Rabone, J.; Yue, Y.-F.; Chong, S. Y.; Stylianou, K. C.; Bacsa, J.;
Bradshaw, D.; Darling, G. R.; Berry, N. G.; Khimyak, Y. Z.; Ganin, A. Y.;
Wiper, P.; Claridge, J. B.; Rosseinsky, M. J. Science 2010, 329, 1053. (b)
Chen, Q.; Chang, Z.; Song, W.-C.; Song, H.; Song, H.-B.; Hu, T.-L.; Bu,
X.-H. Angew. Chem. Int. Ed. 2013, 52, 11550. (c) Mason, J. A.; Oktawiec,
J.; Taylor, M. K.; Hudson, M. R.; Rodriguez, J.; Bachman, J. E.; Gonzalez,
M. I.; Cervellino, A.; Guagliardi, A.; Brown, C. M.; Llewellyn, P. L.;
Masciocchi, N.; Long, J. R. Nature 2015, 527, 357. (d) Deria, P.; Gómez-
Gualdrón, D. A.; Bury, W.; Schaef, H. T.; Wang, T. C.; Thallapally, P. K.;
Sarjeant, A. A.; Snurr, R. Q.; Hupp, J. T.; Farha, O. K. J. Am. Chem. Soc.
2015, 137, 13183. (e) Krause, S.; Bon, V.; Senkovska, I.; Stoeck, U.;
Wallacher, D.; Többens, D. M.; Zander, S.; Pillai, R. S.; Maurin, G.;
Coudert, F.-X.; Kaskel, S. Nature 2016, 532, 348.
(3) (a) Kawamichi, T., Haneda, T.; Kawano, M.; Fujita, M. Nature 2009, 461,
633. (b) Das, R. K.; Aijaz, A.; Sharma, M. K.; Lama, P.; Bharadwaj, P. K.
Chem.-Eur. J. 2012, 18, 6866.
(4) (a) Feng, X.; Ding, X.; Jiang, D. Chem. Soc. Rev. 2012, 41, 6010. (b) Ding,
S.-Y.; Wang, W. Chem. Soc. Rev. 2013, 42, 548. (c) Colson, J. W.; Dichtel,
W. R. Nat. Chem. 2013, 5, 453. (d) Segura, J. L.; Mancheño, M. J.;
Zamora, F. Chem. Soc. Rev. 2016, 45, 5635.
(5) (a) Diercks, C.; Yaghi, O. M. Science 2017, 355, 923. (b) Liu, Y.; Ma, Y.;
Zhao, Y.; Sun, X.; Gándara, F.; Furukawa, H.; Liu, Z.; Zhu, H.; Zhu, C.;
Suenaga, K.; Oleynikov, P.; Alshammari, A. S.; Zhang, X.; Terasaki, O.;
Yaghi, O. M. Science 2016, 351, 6271.
(6) Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keeffe, M.; Matzger, A. J.;
Yaghi, O. M. Science 2005, 310, 1166.
(7) Uribe-Romo, F. J.; Hunt, J. R.; Furukawa, H.; Klöck, C.; O’Keeffe, M.;
Yaghi, O. M. J. Am. Chem. Soc. 2009, 131, 4570.
(8) Zhang, Y.-B.; Su, J.; Furukawa, H.; Yun, Y.; Gándara, F.; Duong, A.; Zou,
X.; Yaghi, O. M. J. Am. Chem. Soc. 2013, 135, 16336.
(9) Henke, S.; Schneemann, A.; Wütscher, A.; Fischer, R. A. J. Am. Chem. Soc.
2012, 134, 9464.
(10) Harada, J.; Ogawa, K. Chem. Soc. Rev. 2009, 38, 2244.
(11) (a) Fraissard, J.; Ito, T. Zeolites 1988, 8, 350. (b) Bonardet, J.-L.; Fraissard,
J.; Gédéon, A.; Springuel-Huet, M.-A. Catal. Rev. 1999, 41, 115.
(12) Succesful applications in characterzing flexbile MOFs: (a) Springuel-Huet,
M.-A.; Nossov, A.; Adem, Z.; Guenneau, F.; Volkringer, C.; Loiseau, T.;
Férey, G.; Gédéon, A. J. Am. Chem. Soc. 2010, 132, 11599. (b) Hoffmann,
H. C.; Assfour, B.; Epperlein, F.; Klein, N.; Paasch, S.; Senkovska, I.;
Kaskel, S.; Seifert, G.; Brunner, E. J. Am. Chem. Soc. 2011, 133, 8681.
(13) (a) Huang, N.; Chen, X.; Krishna, R.; Jiang, D. Angew. Chem. Int. Ed.
2015, 54, 2986. (b) Huang, N.; Krishna, R.; Jiang, D. J. Am. Chem. Soc.
2015, 137, 7079.
(14) Liao, P.-Q.; Chen, H.-Y.; Zhou, D.-D.; Liu, S.-Y.; He, C.-T.; Rui, Z.-B.; Ji,
H.-B.; Zhang, J.-P.; Chen, X.-M. Energy Environ. Sci. 2015, 8, 1011.
(15) Similar sovlent-induced gating CO2 adsorption has been recently report in
MOFs. See: Carrington, E. J.; McAnally, C. A; Fletcher, A. J.; Thompson,
S. P.; Warren, M.; Brammer, L. Nat. Chem. 2017, ASAP. DOI:
10.1038/NCHEM.2747.
(16) (a) Fang, Q.; Gu, S.; Zheng, J.; Zhuang, Z.; Qiu, S.; Yan, Y. Angew. Chem.
Int. Ed. 2014, 53, 2878. (b) Shinde, D. B.; Kandambeth, S.; Pachfule, P.;
Kumar, R. R.; Banerjee, R. Chem. Commun. 2015, 51, 310. (c) Li, H.; Pan,
Q.; Ma, Y.; Guan, X.; Xue, M.; Fang, Q.; Yan, Y.; Valtchev, V.; Qiu, S. J.
Am. Chem. Soc. 2016, 138, 14783. (d) Sun, Q.; Aquila, B.; Ma, S.-Q.
Mater. Chem. Front. 2017, ASAP. DOI: 10.1039/C6QM00363J.
(17) Khouw, C. B.; Davis, M. E. ACS Symp. Ser. 1993, 517, 206.
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