Structural and Photomagnetic Studies of Two Compounds in the System Cu2+/Mo(CN)84-: From Trinuclear Molecule to Infinite Network
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- 作者：Guillaume Rombaut ; Marc Verelst ; Sté ; phane Golhen ; Lahcè ; ne Ouahab ; Corine Mathoniè ; re ; and Olivier Kahn
- 刊名：Inorganic Chemistry
- 出版年：2001
- 出版时间：March 12, 2001
- 年：2001
- 卷：40
- 期：6
- 页码：1151 - 1159
- 全文大小：147K
- 年卷期：v.40,no.6(March 12, 2001)
- ISSN：1520-510X
文摘
The syntheses and structural and physical characterization of the compounds [Cu(bipy)2]2[Mo(CN)8]·5H2O·CH3OH (1) with bipy = 2,2'-bipyridine and MII2[MoIV(CN)8]·xH2O (2 with M = Cu, x = 7.5; 3 with M = Mn,x = 9.5) are presented. 1 crystallizes in the triclinic space group P
(a = 11.3006(4) Å, b = 12.0886(5) Å, c =22.9589(9) Å, 
= 81.799(2)
, 
= 79.787(2), 
= 62.873(2), Z = 2). The structure of 1 consists of neutraltrinuclear molecules in which a central [Mo(CN)8]4- anion is linked to two [Cu(bipy)2]2+ cations through twocyanide bridges. 2 crystallizes poorly, and hence, structural information has been obtained from the wide-angleX-ray scattering (WAXS) technique, by comparison with 3 and FeII2(H2O)4[MoIV(CN)8]·4H2O whose X-raystructure has been previously solved. 2, 3, and FeII2(H2O)4[MoIV(CN)8]·4H2O form extended networks with allthe cyano groups acting as bridges. The magnetic properties have shown that 1 and 2 behave as paramagnets.Under irradiation with light, they exhibit important modifications of their magnetic properties, with the appearanceat low temperature of magnetic interactions. For 1 the modifications are irreversible, whereas they are reversiblefor 2 after cycling in temperature. These photomagnetic effects are thought to be caused by the conversion ofMoIV (diamagnetic) to MoV(paramagnetic) through a photooxidation mechanism for 1 and a photoinduced electrontransfer in 2. These results have been correlated with the structural features.
(a = 11.3006(4) Å, b = 12.0886(5) Å, c =22.9589(9) Å, = 81.799(2), = 79.787(2), = 62.873(2), Z = 2). The structure of 1 consists of neutraltrinuclear molecules in which a central [Mo(CN)8]4- anion is linked to two [Cu(bipy)2]2+ cations through twocyanide bridges. 2 crystallizes poorly, and hence, structural information has been obtained from the wide-angleX-ray scattering (WAXS) technique, by comparison with 3 and FeII2(H2O)4[MoIV(CN)8]·4H2O whose X-raystructure has been previously solved. 2, 3, and FeII2(H2O)4[MoIV(CN)8]·4H2O form extended networks with allthe cyano groups acting as bridges. The magnetic properties have shown that 1 and 2 behave as paramagnets.Under irradiation with light, they exhibit important modifications of their magnetic properties, with the appearanceat low temperature of magnetic interactions. For 1 the modifications are irreversible, whereas they are reversiblefor 2 after cycling in temperature. These photomagnetic effects are thought to be caused by the conversion ofMoIV (diamagnetic) to MoV(paramagnetic) through a photooxidation mechanism for 1 and a photoinduced electrontransfer in 2. These results have been correlated with the structural features.