A Three-Dimensional Metal–Organic Framework with a pcu Net Constructed
By Zinc(II)/3-Amino-1, 2, 4-triazole Layer and an Inorganic Sulfate Pillar
Jian-Di Lin, Zhi-Jian Huang, Yong-Ping Xie, Qing-Lu Li
Reference: MOLSTR 21128
To appear in: Journal of Molecular Structure
Received Date: 10 September 2014
Revised Date: 21 November 2014
Accepted Date: 21 November 2014
Please cite this article as: J-D. Lin, Z-J. Huang, Y-P. Xie, Q-L. Li, A Three-Dimensional Metal–Organic Framework with a pcu Net Constructed By Zinc(II)/3-Amino-1, 2, 4-triazole Layer and an Inorganic Sulfate Pillar, Journal of
Molecular Structure (2014), doi: http://dx.doi.org/10.1016/j.molstruc.2014.11.050
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A Three-Dimensional Metal–Organic Framework with a pcu Net Constructed By Zinc(II)/3-Amino-1, 2, 4-triazole Layer and an Inorganic Sulfate Pillar
Jian-Di Lin a, Zhi-Jian Huang b, Yong-Ping Xie a, Qing-Lu Li*, a,b a
Department of Applied Chemistry, College of Life Sciences, Fujian Agriculture and
Forestry University, Fuzhou, Fujian 350002, P. R. China.
E-mail: firstname.lastname@example.org; Tel: +0086-591-83750182; Fax: 0086-591-83789352. b Fujian Provincial Engineering Laboratory of Animal Pharmaceuticals, College of
Animal Science, Fujian Agriculture and Forestry University, Fuzhou, Fujian 350002,
P. R. China.
Hydrothermal reaction of ZnSO4·7H2O and 3-amino-1H-1, 2, 4-triazole (HATRZ) led to a three-dimensional zinc(II) coordination polymer, Zn2(ATRZ)2SO4·3H2O (1).
Compound 1 has been fully characterized by single crystal and powder X-ray diffraction, thermogravimetric analysis, infrared spectroscopy and elemental analysis.
Single crystal X-ray diffraction reveals that 1 is a pcu-like network metal-organic framework which is constructed by a zinc(II)/ATRZ layer and a rarely reported inorganic sulfate pillar. Moreover, 1 shows characteristic ligand-centered fluorescence property.
Keywords: Coordination Polymer; Inorganic Sulfate Pillar; Crystal structure;
Topological analysis; Photoluminescent.
Nowadays great interest has been focused on the design and synthesis of metal-organic frameworks (MOFs) due to their intriguing topological structures and 2 potential applications in gas storage and separation, magnetism, luminescence, and catalysis [1-4]. Although many MOFs have been successfully synthesized, true rational control in constructing polymers with desired physical properties still remains a distant prospect in crystal engineering . It is well-known that the nature of organic ligands is crucial for the design and construction of desired MOFs. The architectures and functionality of MOFs are strongly influenced by the flexibility, length, coordination ability and symmetry of the organic ligands [6, 7]. The most commonly ligands used to construct functionalized MOFs are aromatic polycarboxylates and polypyridines because the former can exhibit flexible coordination modes, while the latter can afford more predictable coordination modes.
More recently, polyazaheteroaromatic organic ligands such as pyrazole, imidazole, triazole and tetrazole have been employed in the construction of various functional
MOFs [8-10]. 1H-1, 2, 4-triazole (HTRZ) can be considered as a representative hybrid of both pyrazole and imidazole due to that the angles between N-coordinating atoms are similar to those of both pyrazole and imidazole. It combines the negative charge of carboxylates and predictable coordination modes of pyridines and can exhibit a strong and typical property of acting as bridging ligand among metal centers [11-13]. Thus a number of functional metal-triazolate compounds have been prepared using this ligand [14-17]. Substituted HTRZ ligands have also been employed to create MOFs with fascinating architectures. For example, the application of 3-amino-1H-1, 2, 4-triazole (HATRZ) which possesses all the virtues of HTRZ in the field of coordination chemistry resulted in various functional MOFs such as
Ag6Cl(ATRZ)4(OH)  and ZnF(ATRZ) . Moreover, HATRZ could also be employed as an asymmetrically substituted achiral ligand to build novel chiral compounds when the nitrogen atom of the amino group of HATRZ also participates in coordination. Li et al.  obtained a novel chiral cadmium MOF, CdCl(ATRZ), based on the unsymmetrical achiral ATRZ anion with an unprecedented μ4-bridging mode. Meanwhile, anions also play an important role in the structure control for self-assembly. A considerable range of anions are known to act as bridges in inorganic lattices and organic-inorganic compounds. The frequently used inorganic 3 anion ligands are phosphates [21, 22], halides [23, 24], and sulfate [25-28]. The incorporated inorganic anion ligands do not simply compensate the charge balance, but rather increase the structural complexity and hence functionality. The sulfate ion, as a simple tetrahedral oxoanion, has been found to serve as an auxiliary bridge in the construction of many multidimensional MOFs [29-32]. Although the sulfate ion is known to have very rich coordination modes, such as monodentate, bidentate bridging, bidentate chelating, and tridentate bridging, etc., however, to our surprise, there are extremely rare reports with reference to sulfate-pillared MOF materials until now. To our knowledge, the most related one is [Zn2(μ2-SO4)(μ3-datrz)2]·2H2O (Hdatrz = 3, 5-diamino-1, 2, 4-triazole) which is constructed by the Zn/datrz layers and the inorganic sulfate pillars . The other related one is Ln2(OH)4SO4·nH2O (Ln = Pr to