Inorganic-Metalorganic Hybrids Based on Copper(II)-Monosubstituted Keggin Polyanions and Dinuclear Copper(II)-Oxalate Complexes. Synthesis, X-ray Structural Characterization, and Magnetic Properties
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- 作者：Santiago Reinoso ; Pablo Vitoria ; Juan M. Gutié ; rrez-Zorrilla ; Luis Lezama ; Leire San Felices ; and Javier I. Beitia
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：December 26, 2005
- 年：2005
- 卷：44
- 期：26
- 页码：9731 - 9742
- 全文大小：465K
- 年卷期：v.44,no.26(December 26, 2005)
- ISSN：1520-510X
文摘
Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-bipyridine-oxalatecomplexes in the corresponding alkaline acetate buffer led to the formation of hybrid metal organic-inorganiccompounds K2[{SiW11O39Cu(H2O)}{Cu2(bpy)2(H2O)2(
mages/entities/mgr.gif">-ox)}2]·14H2O (1), K14[{SiW11O39Cu(H2O)}{Cu2(bpy)2(mages/entities/mgr.gif">-ox)}]2[SiW11O39Cu(H2O)]·55H2O (2), (NH4)4[{SiW11O39Cu(H2O)}{Cu2(bpy)2(mages/entities/mgr.gif">-ox)}]·10H2O (3), and Rb4[{SiW11O39Cu(H2O)}{Cu2(bpy)2(mages/entities/mgr.gif">-ox)}]·10H2O (4). Their structures have been established by single-crystal X-ray diffraction.The main structural feature of these compounds is the presence of copper(II)-monosubstituted mages/gifchars/alpha.gif" BORDER=0>-Keggin polyoxoanionsas inorganic building blocks, on which the mages/entities/mgr.gif">-oxalatodicopper metalorganic blocks are supported. Compound 1contains the discrete hybrid polyanion [{SiW11O39Cu(H2O)}{Cu2(bpy)2(H2O)2(mages/entities/mgr.gif">-ox)}2]2-, whereas the polymerichybrid polyanion [{SiW11O39Cu(H2O)}{Cu2(bpy)2(mages/entities/mgr.gif">-ox)}2]n4n- gives a monodimensional character to compounds2-4. Magnetic and EPR results are discussed with respect to the crystal structure of the compounds. DFT calculationson both the [Cu2(bpy)2(H2O)4(mages/entities/mgr.gif">-ox)]2+ cationic complex and the metalorganic blocks have been performed in orderto determine the optimized geometry and the magnetic coupling constants, respectively.