Abstract

Eight new metal–organic hybrid materials, namely {Cd(Tcph)(4,4′-bipy)1/2}

(1), {[Cd2(Tcph)2(1,4-bimb)1/2(H2O)4]·H2O} (2), {Cd2(Tcph)2(1,4-
bmimb)1/2(H2O)4} (3), {Cd(Tcph)(1,2-bmimb)} (4), {Cu(Tcph)(1,4-bimb)(H2O)}
(5), {[Co(Tcph)(1,4-bimb)1/2(H2O)3]·(H2O)} (6), {Zn(Tcph)(1,2-bimb)} (7),
{Cu2(Tcph)2(1,2-bimb)(H2O)4} (8), where Tcph=tetrachlorophthalate acid,
4,4′-bipy=4,4′-bipyridine, 1,4-bimb=1,4-bis(imidazol-1-ylmethyl)benzene,
1,4-bmimb=1,4-bis(2-methylimidazol-1-ylmethyl)benzene, 1,2-bimb=1,2-
bis(imidazol-1-ylmethyl)-benzene, 1,2-bmimb=1,2-bis(2-methylimidazol-1-
ylmethyl)benzene, have been synthesized and characterized. Their
structures are determined by single crystal X-ray diffraction and further
characterized by infrared spectra (IR) and thermogravimetric (TG) analyses.
Complex 1, 4 and 7 display 2D layer structures. 1 possesses two-
dimensional sheet containing an unusual [Cd(Tcph)] chains linked by 4,4′-
bipy co-ligand, while 4 and 7 hold the similar 4-connected 44-sql nets.
Complex 2 and 3 feature a similar three dimensional (3D) internal
compensation structure with a topology of {4 2·63·8}2{63}. 5 is a novel 2-fold
self-penetrating 3D network with 4-coordinated 65·8–CdSO4 subnets. The
ladder-like chains of 6 are further connected through O–H···O interactions to
yield a 3D supramolecular structure. 8 is a discrete tetranuclear complex.
The thermal stabilities of 1–8 and the luminescent properties of 1–4 and 7 in
the solid state are also discussed.
Graphical abstract
Structure diversity and photoluminescence of eight new metal–
organic hybrid materials constructed by Tetrachlorophthalate acid and
different N-donor coligands are discussed in the context.

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Introduction
Metal–organic hybrid materials built from transition metal ions and organic
bridging ligands has attracted great attention within the scientific
community, not only for their intriguing structural diversity based on
supramolecular assemblies, but also for their great potential as electrical and
optical functional materials, porous materials, and heterogeneous
catalysts, etc. [1], [2], [3]. The compositional/structural diversities of metal–
organic hybrid materials may be tuned by a shrewd choice of organic
ligands, systematically adjusting coordination tendencies of metal ions under
suitable synthesis conditions as well as the use of templates (or structure-
directing agents). In particular, the similar organic ligands with poor or
inactive substituent group, such as –halogen –alkyl, –OH, –NO 2, –NH2, and –
OCH3, may sometimes result in completely different framework structures
because of the extreme sensitivity of self-assembly [4], [5], [6]. In this
regard, ligands with common geometry configuration also have chance to
find their new niche in the employ of crystal engineering method. For
example, a family of metal–organic hybrid materials based on perfluorinated
benzenedicarboxylate have been synthesized by Anthony K. C. group. Their
results show no structures containing fluorinated dicarboxylates that are
isostructural to any structures containing the respective nonfluorinated
analogs [5]. Based on the above reasons, we believes that new metal–
organic hybrid materials with varied structures and topologies could still be
achieved by employed halogenated carboxylate ligands. Because of the
significantly enhanced acidity and steric hindrance and the potential weak
intermolecular interaction (Halogen···Halogen interactions [7], [8], [9], C–
H···Halogen interactions [10], C–Halogen···Metal interactions [11], etc.), it is
also effective to introduce auxiliary N-donor linkers in preparing mixed
ligands coordination complexes with higher-dimensional structures and novel
topologies, which have been proven by us as well as many other groups [12].
Naturally, the employment of N-donor mixed ligands in the self-assembly
process has gradually become a universal and effective approach to obtain
novel frameworks, which have been reviewed by Miao's group [13].
To further understand the chemical tendency of halogenated carboxylate
acid and synergistic effect of mixed-ligand in self-assembly process and to
prepare novel materials with beautiful architectures and good physical
properties, herein we employed the functional group substituted phthalate
(Cl4-H2bdc) as ligand and a series of bidentate N-donor molecule (4,4′-bipy,
1,4-bimb, 1,4-bmimb, 1,2-bimb, 1,2-bmimb) (Cl 4-
H2bdc/Tcph=tetrachlorophthalate acid, 4,4′-bipy=4,4′-bipyridine, 1,4-
bimb=1,4-bis(imidazol-1-ylmethyl)benzene, 1,4-bmimb=1,4-bis(2-
methylimidazol-1-ylmethyl)benzene, 1,2-bimb=1,2-bis(imidazol-1-ylmethyl)-
benzene, 1,2-bmimb=1,2-bis(2-methylimidazol-1-ylmethyl)benzene) as co-
ligands. Eight new metal–organic hybrid materials have been obtained under
solvothermal conditions: {Cd(Tcph)(4,4′-bipy)1/2} (1), {[Cd2(Tcph)2(1,4-
bimb)1/2(H2O)4]·H2O} (2), {Cd2(Tcph)2(1,4-bmimb)1/2(H2O)4} (3), {Cd(Tcph)(1,2-
bmimb)} (4), {Cu(Tcph)(1,4-bimb)(H2O)} (5), {[Co(Tcph)(1,4-
bimb)1/2(H2O)3]·(H2O)} (6), {Zn(Tcph)(1,2-bimb)} (7), {Cu2(Tcph)2(1,2-bimb)
(H2O)4} (8). The thermal stabilities of 1–8 and the luminescence properties
of 1-4 and 7 in the solid state are also discussed (Scheme 1).
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Section snippets
General materials and methods
All reagents, chemicals, and solvents were purchased from commercial
sources and used without any further purification. The ligand 1,4-bimb=1,4-
bis(imidazol-1-ylmethyl)benzene, 1,4-bmimb=1,4-bis(2-methylimidazol-1-
ylmethyl)benzene, 1,2-bimb=1,2-bis(imidazol-1-ylmethyl)-benzene, 1,2-
bmimb=1,2-bis(2-methylimidazol-1-ylmethyl)benzene were prepared
according to the previously published literature procedures [14]. IR of
supramolecular samples were recorded with a Nicolet Impact 410 FTIR
spectrometer
{Cd(Tcph)(4,4′-bipy)1/2}n (1)
The result of X-ray diffraction analysis reveals that complex 1 shows a
fantastic 2-D layer. The asymmetric unit of 1 contains one divalent cadmium
ion, one Tcph2− anion and a half of 4,4′-bipy ligand. As shown in Fig. 1a, the
center Cd atom is octahedral coordination sphere coordinated by five
carboxyl group oxygen atoms from four different Tcph ligand (Cd–O=2.255–
2.332 Å), one Npyridine atom (Cd–N=2.30 Å), which indicates the similar
coordinative abilities of both Ocarboxyl and Npyridine atoms.
Conclusions
Eight new Cd(II), Cu(II), Zn(II) and Co(II) metal–organic hybrid materials with
different structures have been isolated through varying the N-containing co-
ligands and metal centers. The structures of N-containing co-ligands and the
geometries of the central metals have a great influence on their
structures. 1 exhibits an rare 1D Tcph-Cd chain which are further linked by
4,4′-bipy ligands to form the final 2D layer. Complexes 2, 3 and 5 display 3D
frameworks, while the topologies of their
Acknowledgments
This work was financially supported by the National Natural Science
Foundation of China (Nos. 51372125, 21371105, and 21203106), and
the Scientific and Technical Development Project of Qingdao (No. 13-1-4-184-
jch).
Research data for this article

Cambridge Crystallographic Data Center

Crystallographic data
Data associated with the article:
CCDC 1034544: Experimental Crystal Structure Determination
CCDC 1034538: Experimental Crystal Structure Determination
CCDC 1034541: Experimental Crystal Structure Determination
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