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Issue 12, 2010
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Anion-dependent construction of copper(i/ii)-1,2,4,5-tetra(4-pyridyl)benzene frameworks

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The unique tetrapyridyl ligand 1,2,4,5-tetra(4-pyridyl)benzene (bztpy) isolated from previous hydrothermal in situ metal ligand reaction is found to exhibit remarkable anion-dependent assembly of a series of novel metal–organic frameworks (MOFs), [Cu2(CN)2(bztpy)] (1), [Cu(SO4)(bztpy)]·1.5H2O (2), [Cu2Br2(bztpy)]·MeCN (3) and [Cu10I10(bztpy)2]·2H2O (4), which were synthesized under hydro/solvothermal conditions. These MOFs were characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1 consists of [Cu(CN)]n chains that link the neighbouring ones via tetradentate bztpy bridges to form a corrugated 2D layer. When bztpy is treated with CuSO4, a 3D (3,5)-connected network 2 is obtained, in which novel [Cu(bztpy)]n ladders are interconnected by sulfate anions μ-bridges. However, Br and I anions assist the formation of {Cu2Br2} and {Cu10I10} SBU in the cluster-based metal–organic frameworks 3 and 4, respectively, and result in a completely different topology. Compound 3 shows a 3D PtS net, while compound 4 has a new 3D (4,8)-connected topology. A discussion of the crystal structures, as well as the coordination behaviour of the special tetrapyridyl ligand upon different geometries of the central connecter is provided. In addition, the photoluminescent properties of 1, 3 and 4 in the solid state at ambient temperature are also investigated.

Graphical abstract: Anion-dependent construction of copper(i/ii)-1,2,4,5-tetra(4-pyridyl)benzene frameworks

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Article information

27 Apr 2010
11 Jun 2010
First published
16 Aug 2010

CrystEngComm, 2010,12, 4378-4385
Article type

Anion-dependent construction of copper(I/II)-1,2,4,5-tetra(4-pyridyl)benzene frameworks

S. Hu, Z. Zhang, Z. Meng, Z. Lin and M. Tong, CrystEngComm, 2010, 12, 4378
DOI: 10.1039/C0CE00141D

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