| In this paper, five novel V-O and V-P-O inorganic-organic hybrid materials [{Mn(phen)2}2V4O12]·1/2H2O 1,[{Co(phen)2}2V4O12]·H2O 2,[Zn(2,2'-bipy)3]3[V15O36Cl)·3H2O 3,[Co(2,2'-bipy)3]3[V15O36Cl]·3H2O 4,(V4O7(HPO4)2(2,2'-bipy)2] 5 have been hydrothermally synthesized through moditying synthetic conditions and starting materials. Structures of the five complexes have been determined by single crystal X-ray diffraction, and the influencing factors on V-O and V-P-O framework have been discussed. Both complexes 1 and 2 are bimetallic cluster complexes which are composed of discrete V40i24" clusters covalently attached to two [M(phen)2]2+ ( M = Mn, Co ) fragments. The V4Oi24" clusters in the two complexes possess different structures, which exhibit chair-like configuration in complex 1 while boat-like configuration in complex 2. In these two complexes, the discrete bimetallic clusters are further extended into interesting three-dimensional supermolecular arrays via n-n stacking interactions of phen groups. Complexes 3 and 4 are two cage-like mixed-valent polyoxovanadates, which possess the same oxo vanadium clusters composed of spherical [VIV8VV7036C1]6" cage with a Cl" ion encapsulated. Complexe 5 is a layered vanadium phosphate, which exhibits an unique 4,6,8-net structure with organonitrogen donors of 2,2'-bipy ligand directly coordinated to the vanadium phosphate framework. The adjacent layers of this complexes are stably packed together to form an interesting 3D supramolecular array through TT-TC stacking interactions between 2,2'-dipy groups. Other characterizations for these five complexes by elemental analysis, IR, ESR and thermal analysis have also been described. |
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