Inorganic-Organic Hybrid Materials Containing Porous Frameworks: Synthesis, Characterization, and Magnetic Properties of the Open Framework Solids [{Co(4,4'-Bipy)}V2O6] and [{Co<
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- 作者：M. Ishaque Khan ; Elizabeth Yohannes ; Renata C. Nome ; Samar Ayesh ; Vladimir O. Golub ; Charles J. O'Connor ; and Robert J. Doedens
- 刊名：Chemistry of Materials
- 出版年：2004
- 出版时间：December 14, 2004
- 年：2004
- 卷：16
- 期：25
- 页码：5273 - 5279
- 全文大小：466K
- 年卷期：v.16,no.25(December 14, 2004)
- ISSN：1520-5002
文摘
Synthesis of two novel porous framework hybrid materials, [Co(4,4'-bipy)V2O6] (1) and[{Co2(4,4'-bipy)3(H2O)2}V4O12]·2H2O (2), and their characterization by infrared spectroscopy,thermogravimetry, elemental analysis, manganometric titration, surface area measurement,bond valence sum calculations, temperature-dependent magnetic susceptibility measurement,and single-crystal X-ray structure analyses is described. Both compounds exhibit remarkablethermal stability. The three-dimensional structures of 1 and 2 are composed of fused {VO4}motifs linked by {Co(4,4'-bipy)} coordination polymers. The structure of 1 is comprised of{CoO3N2} trigonal bipyramids, linked in two dimensions by corner-sharing {VO4} tetrahedraand in the third dimension by the 4,4'-bipyridine ligands. In the bimetallic layers, the cobaltcenters are bridged alternately by {VO4} and {V2O7} units, generating alternating eight-membered {Co2V2O4} and twelve-membered {Co2V4O6} rings. The crystal structure of 2consists of a novel three-dimensional network containing two types of octahedral Co2+ ionslinked by a {V2O7} group. The cobalt centers in 2 are linked in three dimensions by bridging4,4'-bipyridine ligands. The structure contains rather large channels parallel to the c-axis.A disordered water molecule of crystallization is present in the channels. Crystal data forC10H8N2O6CoV2, 1: triclinic space group P
(No. 2), a = 8.1517(4) Å, b = 8.5794(4) Å, c =10.1233(5) Å, 
= 87.0170(10)
, 
= 75.9610(10), 
= 75.1740(10), V = 663.94(6) Å3, Z =2, Dcalcd = 2.066 Mg·m-3, R1 = 0.0252 (all data), wR2 = 0.0669. Crystal data for C15H16N3O8CoV2, 2: monoclinic space group C2/c (No. 15), a = 30.4457(13) Å, b = 11.3540(5) Å, c =11.5836(5) Å, = 106.5390(10), V = 3838.6(3) Å3, Z = 8, Dcalcd = 1.824 Mg·m-3, final R1 =0.0447 (all data), wR2 = 0.1259.
(No. 2), a = 8.1517(4) Å, b = 8.5794(4) Å, c =10.1233(5) Å, = 87.0170(10), = 75.9610(10), = 75.1740(10), V = 663.94(6) Å3, Z =2, Dcalcd = 2.066 Mg·m-3, R1 = 0.0252 (all data), wR2 = 0.0669. Crystal data for C15H16N3O8CoV2, 2: monoclinic space group C2/c (No. 15), a = 30.4457(13) Å, b = 11.3540(5) Å, c =11.5836(5) Å, = 106.5390(10), V = 3838.6(3) Å3, Z = 8, Dcalcd = 1.824 Mg·m-3, final R1 =0.0447 (all data), wR2 = 0.1259.