Hydrothermal syntheses, crystal structures and magnetic properties of two inorganic-organic hybrid materials: [{Cu(phen)}(2)((VO2)-O-V)(2)(VO2)-O-IV(H2O)(PO4)(2)] and [V4O7(2,2 '-bpy)(2)(HPO4)(2)] (phen=1,10-phenathroline, bpy = bipyridine)

摘要

Two two-dimensional inorganic organic hybrid materials formulated as [{Cu(phen)}(2)((VO2)-O-V)(2)(VO2)-O-IV(H2O)(PO4)(2)] 1 and [V4O7(2,2'-bpy)(2)(HPO4)(2)] 2 have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Both crystallize in the triclinic space group P (l) over bar (no. 2), with cell parameters a = 8.118(3), b = 9.272(3), c = 10.348(5) Angstrom, alpha = 96.71(1) beta = 100.97(1), gamma = 104.66(1)degrees, V = 728.5(5) Angstrom(3), Z = 1 for 1 and a = 8.402(4), b = 9.270(5), c = 9.676(7) Angstrom, alpha = 97.10(1), beta = 110.29(1), gamma = 98.92(1)degrees, V = 685.4(7) Angstrom(3), Z = 1 for 2. The structure of 1 is analogous to that of [{Cu(phen)}(2)((VO2)-O-V)(3)(OH)(PO4)(2)] (1') and consists of [{Cu(phen)}(2)(VO6)-O-IV(H2O)](infinity) chains that are bridged by {(VO2)(PO4)}(2) 4-membered rings via oxygen atoms into a two-dimensional network. Compounds 1 and 1' are isostructural but the oxidization states of vanadium atoms in them are not fully same. Thus, 1 and 1' are relatively rare examples of all V(V) and V(V)/V(IV) mixed valence analogues in the solid state. Compound 2 is also relatively uncommon and features 2,2'-bipy ligands directly coordinated to vanadium atoms. The structure of 2 is constructed by 4-, 6- and 8-membered rings and is topologically relevant to [V3O7(phen)]. The temperature-dependent magnetic susceptibility of 1 shows alternating ferro- and antiferromagnetic interactions. (C) 2003 Elsevier Inc. All rights reserved. [References: 50]