Anion-dependent construction of copper(i/ii)-1,2,4,5-tetra(4-pyridyl)benzene frameworksElectronic supplementary information (ESI) available: Crystallographic data, PXRD pattern for 1and 4. CCDC reference numbers 768410(1), 768411(2), 768412(3) and 768413(4). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c0ce00141d

The unique tetrapyridyl ligand 1,2,4,5-tetra(4-pyridyl)benzene (bztpy) isolated from previous hydrothermal in situmetal 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 1consists of [Cu(CN)]nchains that link the neighbouring ones viatetradentate bztpy bridges to form a corrugated 2D layer. When bztpy is treated with CuSO4, a 3D (3,5)-connected network 2is obtained, in which novel [Cu(bztpy)]nladders 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 3and 4, respectively, and result in a completely different topology. Compound 3shows a 3D PtS net, while compound 4has 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, 3and 4in the solid state at ambient temperature are also investigated. [ABSTRACT FROM AUTHOR]