Enantiomerism, diastereomerism and thermochromism in two Cu7I4 cluster-based coordination polymers

Article abstract of DOI:10.1039/c9tc05996b

Solvothermal reaction between CuI and 5-(3-pyridyl)tetrazole (HPTA) in CH₃CN and NH₃·H₂O/n-BuOH, afforded two kinds of Cu₇I₄ cluster-based coordination polymers 1 and 2, respectively. 1 is a racemic conglomerate of enantiomers crystallizing in the P6₃22 space group and 2 is a mesomer crystallizing in the P3c1 group. Both 1 and 2 show dual-channel emissions in which low-energy emission originates from a cluster-centered (CC) excited state while high-energy emission is attributed to an iodide-to-ligand charge transfer (XLCT)/metal-to-ligand charge transfer (MLCT) excited state. Of particular interest, 2 exhibits thermochromic luminescence originating from the combined effects of non-radiative transition and thermal deactivation of the XLCT excited state.

Full text of DOI:10.1039/c9tc05996b

View Article Online
View Journal
Journal of
Materials Chemistry C
Materials for optical, magnetic and electronic devices
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: W. Liao, X. Li, Q.
Zeng, Y. Zhong, Y. Yin and J. He, J. Mater. Chem. C, 2019, DOI: 10.1039/C9TC05996B.
Volume
Number
6
5
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
7
February 2018
Pages 911-1266
Journal of
Materials Chemistry C
Materials for optical, magnetic and electronic devices
rsc.li/materials-c
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 2050-7526
PAPER
Nosang V. Myung, Yong-Ho Choa et al.
A
noble gas sensor platform: linear dense assemblies of
a multi-layered
single-walled carbon nanotubes (LACNTs) in
ceramic/metal electrode system (MLES)
rsc.li/materials-c

Please do not adjust margins
Journal of Materials Chemistry C
Page 1 of 6
View Article Online
DOI: 10.1039/C9TC05996B
COMMUNICATION
Enantiomerism, Diastereomerism and Thermochromism in two
Cu7I4 Cluster-Based Coordination Polymers
Wei-Ming Liao,‡a Xiang-Nan Li,‡b Qi Zeng,a Yuan-Hui Zhong,a Ye-Gao Yinb and Jun He*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Solvothermal reaction between CuI and 5-(3-pyridyl)tetrazole and Cu6I6 CPs based on alkyl-expanding imidazolate ligands
(HPTA) in CH3CN and NH3·H2O/n-BuOH, afforded two kinds of Cu7I4 were also investigated, and they exhibited highly temperature-
cluster-based coordination polymers 1 and 2 respectively. 1 is a dependent luminescence with large red-shifts originating from
racemic conglomerate of enantiomers crystallizing in a P6322 Cu···Cu distance.14. Importantly, CuIICuI15I17 cluster, reported
ퟑ
space group and 2 is a mesomer crystallizing in a P c1 group. Both by our group, represents one of the largest CuxIy-based
1 and 2 show dual-channel emissions in which low-energy clusters in CPs to date and the corresponding 3D mixed-valent
emission originates from cluster centered (CC) excited state while CP showed interesting thermochromic characteristics.2 Up to
high-energy emission is attributed to iodide-to-ligand charge now, development of huge copper iodide clusters with
transfer (XLCT)/metal-to-ligand charge transfer (MLCT) excited desirable photoluminescent and thermochromic properties is
state. Of particular interest,
2
exhibits thermochromic still a challenging and demanding task. Generally, the self-
luminescence originating from the combined effects of non- assembly of functionally designed CuxIy-based CPs are
radiative transition and thermal deactivation of XLCT excited state. influenced not only by the coordination modes of ligands, but
also susceptible to non-structural parameters, e.g.
Copper iodide clusters, the inorganic aggregates generally
formulated as CuxIy, have attracted a long-lasting attention in
coordination chemistry.1-4 In the past two decades, the copper
iodide cluster in combination with various ligands have led to a
number of complexes exhibiting vivid luminosity rooted in
intra-cluster metal-halide charge transfer and cluster-centered
temperature, types of solvent, and choice of additives, etc.
Regulating these parameters gives copper iodide clusters with
various structures and thermodynamic properties.3 Therefore,
it is necessary to design methodology to manipulate tunable
copper iodide clusters and appropriate ligands for fabricating
photoresponsive CPs. In addition, even though chiral copper
iodide clusters are of great potential in construction of
enantioselective reactors, sieves, catalysts and sensors,
research on this area is rare.15-17
6
interaction.5, Lately, these complexes have been used as
building blocks to fabricate functional coordination polymers
(CPs) for advanced applications in sensors, photovoltaic
devices and white-light-emitting materials, etc.7-9
The prepossessing CuxIy-based CPs 1 and 2were obtained
19
from reaction between CuI and 5-(3-pyridyl) tetrazole18,
As a part of this effort, some CuxIy-based CPs achieved from
reactions between CuI and polypyrazole ligands have been
synthesized through solvothermal strategy, and their intrinsic
(HPTA) in CH3CN and n-BuOH/NH3·H2O, respectively. Crystal
structures of 1 and 2 were resolved by single-crystal X-ray
diffraction (SCXRD) while their bulk purities were validated by
powder X-ray diffraction (PXRD) (Fig. S1†). Structural analysis
of 1 revealed that the resultant crystals, crystallizing in a chiral
P6322 space group, are conglomerate of enantiomers (1P and
photoluminescent properties were further investigated.10, 11
A
Cu4I4 cubane coordination polymer based on pyrazolate was
synthesized and found to exhibit dual emissive and
thermochromic luminescence which results from two
competitive excited states.12 Two other Cu4I4-imidazole
pseudopolymorphs reported by Wu et al.13 showed tunable
single cluster-centered triplet emission. Two entangled Cu4I4
1M) with
a formula of [Cu7I4(PTA)3]n for coordination
aggregates. Specifically, P denotes the right-handed helix or
Cu7I4 cluster whereas M denotes the left-handed helix or Cu7I4
cluster. On the other hand, 2 is a meso condensate crystallizing
3
in an achiral P c1 space group with
a formula of
a. School of Chemical Engineering and Light Industry, Guangdong University of
Technology, Guangzhou 510006, China. E-mail: junhe@gdut.edu.cn
b. Department of Chemistry, Shantou University, Shantou 515063, China.
† Electronic Supplementary Information (ESI) available: Experimental details and
synthesis/characterization of MOFs. CCDC 1914081-1914085. For ESI and
crystallographic data in CIF see DOI: 10.1039/x0xx00000x
{[Cu7I4(PTA)3(NH3)]·9H2O}n and has different crystal packing
when compared with other structures prepared in
ethanol/NH3·H2O mixture20. It is noteworthy that 1 and 2
isolated in this work represent the first examples of Cu7I4-
containing CPs demonstrating solvent-induced enantiomerism
‡ These authors contributed equally to this work.
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry C
Page 2 of 6
COMMUNICATION
Journal Name
View Article Online
DOI: 10.1039/C9TC05996B
Fig. 1 The hierarchical assembly scheme of 1M: (a) diagrams of metal salt and ligand molecule, (b) a unique unit, (c) a helix formed from the unique units (top)
and a triple strand formed from helices (below), (d) a view of 1M along c, showing the double-walled channels (e) a topologic equivalent of 1M and (f) the side
(upper) and top (lower) views of 1M-Cu7I4 clusters (Cu red, I green, N blue and C black).
and
disastereomerism
along
with
thermochromic an enantioselective supramolecular programming of a Cu7I4-
based CP. If PTAs and Cu7I4 are taken as linkers and nodes
photoluminescence.
To show the assembly logic of 1, the hierarchical structure of respectively, the CP can be simplified into an unprecedented
1M is taken for discussion below. The crystallographically highly-connected (42·6)(418·615·83) topologized binodal (ns3/ns9
asymmetric unit of 1M consists of one PTA, two iodide and = 2:1) network (Fig. 1f).21 1P, an enantiomer of 1M, exhibits
three CuI atoms in which the Cu3 lies on a C3 axis with site the same coordination behavior and network structure as 1M
occupancy of 0.333 (Fig. 1b). The [Cu3I2] units are connected but possesses right-handed helices constructed from right-
by Cu-N bonds with N4 and N5 from PTA linkers and give the handed conformational ligands clusters (Fig. S2†).
[Cu3I2(PTA)]n helices with a pitch of 65.70 Å (Fig. 1c). The
helices are intertwisted each three to render the triple strands optical isomers crystallizing in a chiral P6322 space group. Two
which integrate through sharing I1 and Cu3, leading to a more randomly selected crystals of have also been
As aforementioned, 1 was isolated as conglomerate of
1
honeycomb-like structure of 1M with an inner diameter of 11 determined by SCXRD and the flack parameters of these three
Å (Fig. 1d). The framework is open, with nanosized chiral crystals achieved from structural refinement were found to be
channels running along c and the theoretic void is calculated various values (Table S1 in Supporting Information). One single
by PLATON program to be 32.7% showing that there is no net crystal possesses a flack value that approximately equals to
interpenetration. Notably, the building units are chiral in zero, indicating the absolute configuration of 1M.22 The other
nature. Specifically, the PTAs are chiral arising from non- two crystals possess non-zero values between 0 and 1,
parallel and non-perpendicular arrangement of pyridyl and implying racemic twinning of 1M and 1P mixture. When
tetrazole rings (dihedral angle: 9.525°, Fig. S2†) while the Cu7I4 circular dichroism (CD) spectrum of 1P crystal was examined,
clusters are chiral stemming from the deviation of I1-Cu2-I2 negative Cotton effect was found in the region of 230-500 nm
planes from I1-Cu3-I2 planes (Fig. 1e). The Cu-I bond lengths (Fig. S3a † ). When 25 randomly selected crystals were
are in the range of 2.622(1) and 2.841(1) Å, and I-Cu-I bond measured, most of the spectra exhibit negative Cotton effect
angles located in the range of 105.77(9) and 118.49(5)°. The indicating enantiopure or enantiomeric excess of 1M in single
Cu···Cu distance is 2.783(1) Å, being shorter than the sum of or twinning crystals (Fig. S3b†). Furthermore, six bulk samples
van der Waals radii of Cu(I) (2.8 Å) and suggesting a modest of parallel experiments have also been measured and unruly
Cu···Cu interaction in the cluster. Obviously, the building units Cotton effect (negative, positive or zero) was found. This
of clusters and ligands are all left-handed in 1M. It is of suggests that various component enantiomer mixtures exist in
fundamental interest to exemplify a chirality transfer from a 1 (Fig. S3c†). To the best of our knowledge, this spontaneous
predetermined ligand to in situ formed metallic motif and generation of enantiomerism is rare in the CuxIy-based CPs
finally to a CP. In this sense, the bottom-up assembly instances achieved from self-assembly of achiral building blocks.10
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
Journal of Materials Chemistry C
Please do not adjust margins
Journal Name
COMMUNICATION
performed to verify the coordination of NH3 to VCieuw(AI)rticclee nOtnelinre.
Absorption peak at 3338 cm-1 with respect to N-H stretching
DOI: 10.1039/C9TC05996B
vibration was clearly observed and is indicative of NH3 present
in 2 (Fig. S5†). The dihedral angle of pyridyl and tetrazole rings
of 2 (8.423°) is slightly smaller than that of 1 (9.525°). Different
solvents in crystal growth may serve as one of the reasons to
account for the morphological differences of copper iodide
clusters in 1 and 2. In this sense, the diastereomerism in 1 and
2 is a genuine solvent-induced metal-ligand-based structural
isomerization. If the Cu7I4 cluster and PTA is denoted as node
and linker, respectively, the racemic CP gives a bimodal
(43)(412·615·89) network, where the nodes present the same
connectivity as those in 1 (Fig. S6†).
Fig. 2 A view of 2 along c axis with the paired conformational isomers of PTAs
Thermal behavior of CP 1 and 2 have also been investigated,
and the thermogravimetric analyses (TGA) curves were
recorded from room temperature to 800 °C (Fig. S7†). For 1,
there is a slight weight loss (about 1.5%) under 300 °C, which
should be ascribed to the crystallized CH3CN molecules. This
argument is consolidated by elemental analysis of 1 (See ESI,
Experimental section). The approximate solvent count was also
verified by residual electrons in the framework with PLATON
program. Subsequent huge weight loss above 300 °C is
attributed to the decomposition of organic ligands. And the
weight loss above 600 °C probably results from the destruction
of inorganic Cu7I4 clusters. For 2, similar to that of 1, the
weight loss (11.4%) under 380 °C probably corresponds to the
water solvents and coordinated NH3 molecules, followed by
the loss of organic ligands. It indicates that both of these two
CPs exhibit good thermo-stability up to 300 °C.
and enantiomers of Cu7I4 clusters highlighted.
In comparison, 2 (at 293 K) is structurally similar to 1 that
PTAs and Cu7I4 clusters construct a honeycomb-like CP with
channels along c direction (Fig. 2). Conformational isomers23 of
PTAs and enantiomers of Cu7I4 clusters (Fig. S4†) were pairwise
observed in 2, showing a totally mesomeric characteristic. The
Cu7I4 clusters in 2 are diastereomeric to those in 1 and have
conformation as urotropin-like cages with Cu3 located outside
the cages. The location of Cu3 ensures the favorable
coordination with NH3, a gas molecule as a donating soft Lewis
base,24 leading to a shorter dCu1···Cu3 of 2.750 Å, suggesting a
strong Cu···Cu interaction in the cluster. (Table S2 in
Supporting Information). The Cu-I bond lengths are in the
range of 2.619(6) and 2.749(6) Å, and I-Cu-I bond angles locate
in the range of 108.58(2) and 116.21(2)°. FT-IR spectrum was
Fig. 3 (a) The solid emission spectra of 1 (λex = 382 nm) and 2 (λex = 380 nm) at 293 K and (b) those of 2 at varied temperatures. (c) The changing trend of HE and
LE of 2 at variable temperatures. (d) The CIE coordinates of emission spectra of 2 at different temperatures.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry C
Page 4 of 6
COMMUNICATION
Journal Name
Expectedly, the above CPs are photo-responsive and give lifetimes of LE and HE of 2 were also measured at various
View Article Online
DOI: 10.1039/C9TC05996B
two emission bands (High-energy emission, HE and low-energy temperatures and fitted with biexponential curves and were
emission, LE) in the range of 450 - 800 nm upon UV-light found to be 0.3-0.4 and 3-5 μs, respectively, corresponding to
irradiation (Fig. 3a). Accordingly, the HE is tentatively assigned phosphorescence (Table S3 in Supporting Information).31
to a iodide-to-ligand charge transfer (XLCT)25/metal-to-ligand According to the CIE coordinates of emission spectra, the
charge transfer (MLCT)26, while the LE probably originates emission color of 2 varies from orange (0.509, 0.405) to
from cluster centered (CC) emission admixed with XMCT and yellow-green (0.353, 0.500) (Fig. 3d). The nature of 2 not only
metal-cluster centered character (MCC: d10 Cu to d9s1 Cu).10 LE represents a new cryogenic effect of copper iodide clusters,
energy of these two CPs (648 nm for 1, 675 nm for 2 at 293 K) but also promises a use of 2 as a low temperature lighting
are close to those of Cu4I4-based complexes (e.g. 645 nm for material.
[(Cu4I4)(MBI)2])13 and this illustrates their similar intra-cluster
excitation. To be noteworthy, the LE band is red-shifted in 2
than 1 and it implies that 2 has a lower energy MCC. This is
Conclusions
probably contributed by the stronger Cu···Cu interaction in 2
than 1 which leads to more influential emission of Cun*
exciplex1, 27, 28. This assumption can be supported by that 2
(dCu1···Cu3 2.750 Å) has a shorter Cu···Cu distance than 1 (2.817
Å for 1P) at 293 K (Table S2 in Supporting Information).
In brief, by the solvothermal reactions between CuI with HPTA
in CH3CN and NH3·H2O/n-BuOH, two honeycomb-like CPs, 1
and 2, with chiral copper iodide clusters as building units were
synthesized respectively. The achieved bulk crystals of 1 were
racemic mixture of optical isomers that reifies enantiomerism
in copper iodide clusters and enantioselective supramolecular
programming of CPs. On the other hand, the isolation of 1 and
2 as diastereomers exemplifies a solvent-induced metal-ligand-
based structural isomerization of CPs and the diastereomerism
in copper iodide clusters. The CPs show dual-channel
The key interest in the emission of copper iodide clusters
rests on the thermo-dependence. As a prototype of CuxIy-
based system, Cu4I4 has been fully studied and found to be
responsive to temperature.29 With the similar emissions of 1
and 2, variable temperature emission spectra of 2 are
selectively measured (Fig. 3b), and it shows that the HE
intensity of 2 enhanced with continuous cooling until 100 K,
while LE intensity increased from 293 K to 170 K and then
slightly decreased to 130 K followed by another increase to
100 K (Fig. 3c). This trend differs from the previously reported
Cu4I4 that usually shows a rise for HE intensity but a decline for
LE with decreasing temperature.30 The monotonous increase
of HE and fluctuating increase of LE intensity upon cooling are
likely the results of multi-factor effect. Firstly, the emission
enhancement of both LE and HE responding to decreasing
temperature is commonly due to reduced non-radiative
transition.31 However, the relative intensity ratio (IHE:ILE) of 2
increases from 0.2 to 1.8 as temperature changes from 293 to
100 K (Fig. S8 † ). This makes HE band dominant at low
temperature while LE band is dominant at room temperature.
The thermal deactivation of XLCT excited state (HE band) is
related to the energy transfer to CC excited state (LE band).32
When cooled from 293 K to 100 K, the LE band of 2 shows an
uncommon blue shift from 675 to 660 nm in contrast to some
reported CuxIy-based CPs which usually exhibit red shift.33, 34 To
elucidate the unusual thermochromism, the crystal structure
of 2 was redetermined at 100 K and it is found that the dCu1···Cu2
distances are almost invariant within the experimental error
though dCu3···Cu1 slightly changed from 2.750 to 2.707 Å (Table
S2 in Supporting Information). This little contraction is
insignificant to affect LE and a shorter dCu···Cu will cause a red
shift of LE emission but not blue shift.14, 35 The result implies
that the energy of LE depends on not only the structure of
ground state, but also that of excited state. Actually a cooling-
induced blue shift of MCC has been found on the d10 M(I)-
pyrazolate trimers and is ascribed to a transformation
between the M-M bounded excited states via solid state
diffusion.36 Accordingly, the blue shift of LE of 2 can be
tentatively assigned to a distortion of d9s1 excited state. The
emissions, and most notably,
2 exhibits manipulatable
luminescence in emission intensity and color through changing
temperature. The demonstrated thermochromism makes
CuxIy-based CPs potential candidates in application of lighting
device and thermal sensor.
This work was supported by the National Natural Science
Foundation of China (21871061, 21901046), Local Innovative
and Research Teams Project of Guangdong Pearl River Talents
Program and Science and Technology Planning Project of
Guangdong Province (2017A050506051), Science and
Technology Program of Guangzhou (201807010026).
Conflicts of interest
There are no conflicts to declare.
References
1
2
3
4
5
E. Cariati, E. Lucenti, C. Botta, U. Giovanella, D. Marinotto and
S. Righetto, Coord. Chem. Rev. , 2016, 306, 566-614.
J. He, J. X. Zhang, C. K. Tsang, Z. Xu, Y. G. Yin, D. Li and S. W. Ng,
Inorg. Chem., 2008, 47, 7948-7950.
P. C. Ford, E. Cariati and J. Bourassa, Chem. Rev., 1999, 99,
3625-3647.
M. Pan, W. M. Liao, S. Y. Yin, S. S. Sun and C. Y. Su, Chem. Rev.,
2018, 118, 8889-8935.
Q. Benito, X. F. Le Goff, S. Maron, A. Fargues, A. Garcia, C.
Martineau, F. Taulelle, S. Kahlal, T. Gacoin, J. P. Boilot and S.
Perruchas, J. Am. Chem. Soc., 2014, 136, 11311-11320.
K. Tsuge, Y. Chishina, H. Hashiguchi, Y. Sasaki, M. Kato, S.
Ishizaka and N. Kitamura, Coord. Chem. Rev. , 2016, 306, 636-
651.
6
7
J. Conesa-Egea, F. Zamora and P. Amo-Ochoa, Coord. Chem.
Rev. , 2019, 381, 65-78.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
Journal of Materials Chemistry C
Please do not adjust margins
Journal Name
COMMUNICATION
8
M. Jayapal, A. Haque, I. J. Al-Busaidi, N. Al-Rasbi, M. K. Al-Suti, 35 Y.-D. Yu, L.-B. Meng, Q.-C. Chen, G.-H. Chen and X.-C. Huang,
View Article Online
M. S. Khan, R. Al-Balushi, S. M. Islam, C. Xin, W. Wu, W. Y.
Wong, F. Marken and P. R. Raithby, Inorg. Chem., 2018, 57, 36 J. X. Zhang, J. He, Y. G. Yin, M. H. Hu, D. Li and X. C. Huang,
New J. Chem. , 2018, 42, 8426-8437.
DOI: 10.1039/C9TC05996B
12113-12124.
Inorg. Chem., 2008, 47, 3471-3473.
9
Z. Wang, C. Y. Zhu, J. T. Mo, P. Y. Fu, Y. W. Zhao, S. Y. Yin, J. J.
Jiang, M. Pan and C. Y. Su, Angew. Chem., Int. Ed., 2019, 58,
9752-9757.
10 W. Liu, Y. Fang and J. Li, Adv. Funct. Mater. , 2018, 28, 1705593.
11 Y. Cheng, P. Xu, Y.-B. Ding and Y.-G. Yin, CrystEngComm, 2011,
13, 2644.
12 S. Z. Zhan, M. Li, X. P. Zhou, J. H. Wang, J. R. Yang and D. Li,
Chem. Commun., 2011, 47, 12441-12443.
13 Z. Fu, J. Lin, L. Wang, C. Li, W. Yan and T. Wu, Cryst. Growth
Des., 2016, 16, 2322-2327.
14 D. Sun, S. Yuan, H. Wang, H. F. Lu, S. Y. Feng and D. F. Sun,
Chem. Commun., 2013, 49, 6152-6154.
15 S. Das, S. Xu, T. Ben and S. Qiu, Angew. Chem., Int. Ed., 2018,
57, 8629-8633.
16 M. Yoon, R. Srirambalaji and K. Kim, Chem. Rev., 2012, 112,
1196-1231.
17 X. Hou, T. Xu, Y. Wang, S. Liu, R. Chu, J. Zhang and B. Liu, ACS
Appl. Mater. Interfaces, 2018, 10, 26365-26371.
18 J.-Q. Sha, J.-W. Sun, C. Wang, G.-M. Li, P.-F. Yan and M.-T. Li,
Cryst. Growth Des., 2012, 12, 2242-2250.
19 Y.-Z. Tang, G.-X. Wang, Q. Ye, R.-G. Xiong and R.-X. Yuan, Cryst.
Growth Des., 2007, 7, 2382-2386.
20 F. Wang, X.-Y. Wu, R.-M. Yu and C.-Z. Lu, Inorg. Chem. Commun.
, 2012, 17, 169-172.
21 V. A. Blatov, A. P. Shevchenko and D. M. Proserpio, Cryst.
Growth Des., 2014, 14, 3576-3586.
22 D. Luo, X.-Z. Wang, C. Yang, X.-P. Zhou and D. Li, J. Am. Chem.
Soc., 2017, 140, 118-121.
23 J. P. Zhang, X. C. Huang and X. M. Chen, Chem. Soc. Rev., 2009,
38, 2385-2396.
24 J. Sun, F. Dai, W. Yuan, W. Bi, X. Zhao, W. Sun and D. Sun,
Angew. Chem., Int. Ed., 2011, 50, 7061-7064.
25 L.-P. Liu, R. Zhang, L. Liu, X.-X. Zhong, F.-B. Li, L. Wang, W.-Y.
Wong, G.-H. Li, H.-J. Cong, N. S. Alharbi and Y. Zhao, New J.
Chem. , 2019, 43, 3390-3399.
26 S. Z. Zhan, W. Chen, W. Lu, J. Zheng, F. Ding, T. Feng and D. Li,
Inorg. Chem., 2018, 58, 1081-1090.
27 Vorontsov, II, A. Y. Kovalevsky, Y. S. Chen, T. Graber, M.
Gembicky, I. V. Novozhilova, M. A. Omary and P. Coppens,
Phys. Rev. Lett. , 2005, 94, 193003.
28 M. A. Omary, M. A. Rawashdeh-Omary, M. W. Gonser, O.
Elbjeirami, T. Grimes, T. R. Cundari, H. V. Diyabalanage, C. S.
Gamage and H. V. Dias, Inorg. Chem., 2005, 44, 8200-8210.
29 C. d. Tard, S. Perruchas, S. b. Maron, X. F. Le Goff, F. o. Guillen,
A. Garcia, J. Vigneron, A. Etcheberry, T. Gacoin and J.-P. Boilot,
Chem. Mater., 2008, 20, 7010-7016.
30 S. Perruchas, X. F. Le Goff, S. Maron, I. Maurin, F. Guillen, A.
Garcia, T. Gacoin and J. P. Boilot, J. Am. Chem. Soc., 2010, 132,
10967-10969.
31 S. Z. Zhan, M. Li, S. W. Ng and D. Li, Chem. Eur. J., 2013, 19,
10217-10225.
32 S. Y. Yin, Z. Wang, Z. M. Liu, H. J. Yu, J. H. Zhang, Y. Wang, R.
Mao, M. Pan and C. Y. Su, Inorg. Chem., 2019, 58, 10736-10742.
33 Y. Wu, X. Zhang, Y. Q. Zhang, M. Yang and Z. N. Chen, Chem.
Commun., 2018, 54, 13961-13964.
34 B. Li, H.-T. Fan, S.-Q. Zang, H.-Y. Li and L.-Y. Wang, Coord. Chem.
Rev. , 2018, 377, 307-329.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Journal of Materials Chemistry C
Page 6 of 6
View Article Online
DOI: 10.1039/C9TC05996B
Reactions of CuI and 5-(3-pyridyl)tetrazole in CH3CN and n-BuOH/NH3H2O gave respectively
the dual-channel emissive coordination polymers, 1 as a conglomerate of enantiomers and 2 as a
meso condensate which exhibits thermochromic luminescence.
1