Valence tautomerism interconversion triggers transition to stable charge distribution in solid polymeric cobalt-polyoxolene complexes
Valence tautomerism interconversion triggers transition to stable charge distribution in solid polymeric cobalt-polyoxolene complexes
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DOI：
10.1039/b710493f
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发表时间：
2007-01-01
影响因子：
4
通讯作者：
Sorace, Lorenzo
中科院分区：
文献类型：
--
作者：
Affronte, Marco;Beni, Alessandra;Sorace, Lorenzo
3，3，3 ′，3 ′-四甲基-5，5 ′，6，6 ′-四羟基-1，1 ′-螺-双（茚满）L与钴盐在二嗪配体存在下的反应提供通式[CoL（二嗪）]（无限）中心点nH（2）O的聚合衍生物，L作为混合价SQ-Cat物种配位。的联吡啶和邻菲咯啉衍生物已通过磁性，EPR和量热测量的装置，其特征在于。表征表明，这两个系统中获得的亚稳态电荷分布，大概是由于我类字符的混合价形式的配体被困。熵驱动的价互变异构体的发生诱导过渡到最稳定的电荷分布。光磁特性表明，化合物的价态互变异构过程是光诱导的，并且在低产率下得到的光诱导亚稳态的寿命约为1000年。2 x 10（5）s，9 K。
The reaction of 3,3,3', 3'-tetramethyl-5,5',6,6'-tetrahydroxy-1,1'spiro-bis(indane), L, with cobalt salts in the presence of diazine ligands affords polymeric derivatives of general formula [CoL(diazine)](infinity)center dot nH(2)O, L being coordinated as a mixed-valence SQ-Cat species. The bipiridyl and o-phenantroline derivatives have been characterised by means of magnetic, EPR and calorimetric measurements. The characterisation showed that both systems are obtained in a metastable charge distribution, presumably trapped due to the class I character of the mixed valence form of the ligand. The occurrence of entropy-driven valence tautomeric interconversion induces the transition to the most stable charge distribution. The photomagnetic characterisation evidenced that valence tautomeric process can be photoinduced and that the lifetime of the photoinduced metastable state, obtained in low yield, is of ca. 2 x 10(5) s at 9 K.