首页> 外文期刊>Chemistry: A European journal >Spectroelectrochemical studies on mixed-valence states in a cyanide-bridged molecular square, [(Ru2Fe2II)-Fe-II(mu-CN)(4)(bpy)(8)](PF6)(4)center dot CHCl3 center dot-H2O
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Spectroelectrochemical studies on mixed-valence states in a cyanide-bridged molecular square, [(Ru2Fe2II)-Fe-II(mu-CN)(4)(bpy)(8)](PF6)(4)center dot CHCl3 center dot-H2O

机译:氰化物桥联的分子正方形[[Ru2Fe2II)-Fe-II(mu-CN)(4)(bpy)(8)](PF6)(4)中心点CHCl3中心点-的混合价态的光谱电化学研究水

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A cyanide-bridged molecular square of [(Ru2Fe2II)-Fe-II(mu-CN)(4)(bpy)(8)]-(PF6)(4).CHCl3.H2O, abbreviated as [(Ru2Fe2II)-Fe-II](PF6)(4), has been synthesised and electrochemically generated mixed-valence states have been studied by spectroelectrochemical methods. The complex cation of [(Ru2Fe2II)-Fe-II](4+) is nearly a square and is composed of alternate Ru-II and Fe-II ions bridged by four cyanide ions. The cyclic voltammogram (CV) of [(Ru2Fe2II)-Fe-II](PF6)(4) in acetonitrile showed four quasireversible waves at 0.69, 0.94, 1.42 and 1.70V (vs. SSCE), which correspond to the four one-electron redox processes of [(Ru2Fe2II)-Fe-II](4+) reversible arrow [(Ru2FeFe)-Fe-II-Fe-II (III)] (5+)reversible arrow[(Ru2Fe2III)-Fe-II](6+) reversible arrow [(RuRuFe2III)-Ru-II-Fe-III](7+) reversible arrow[(Ru2Fe2III)-Fe-III](8+). Electrochemically generated [(Ru2FeFeIII)-Fe-II-Fe-II](5+) and [(Ru2Fe2III)-Fe-II](6+) showed new absorption bands at 2350 nm (epsilon = 5500m(-1) cm(-1)) and 1560 nm (epsilon = 10500 m(-1) cm(-1)), respectively, which were assigned to the intramolecular IT (intervalence transfer) bands from Fell to Fe-III and from Ru-II to Fe-III ions, respectively. The electronic interaction matrix elements (H-AB) and the degrees of electronic delocalisation (alpha(2)) were estimated to be 1090 cm(-1) and 0.065 for the [(Ru2FeFe2III)-Fe-II-Fe-II](5+) state and 1990 cm(-1) and 0.065 for the [(Ru2Fe2III)-Fe-II](6+) states. [References: 44]
机译:[(Ru2Fe2II)-Fe-II(mu-CN)(4)(bpy)(8)]-(PF6)(4).CHCl3.H2O的氰化物桥接分子平方,缩写为[(Ru2Fe2II)-Fe -II](PF6)(4),已经合成,并且通过光谱电化学方法研究了电化学产生的混合价态。 [(Ru2Fe2II)-Fe-II](4+)的复合阳离子几乎为正方形,由交替的Ru-II和Fe-II离子由四个氰化物离子桥连而成。 [(Ru2Fe2II)-Fe-II](PF6)(4)在乙腈中的循环伏安图(CV)显示四个准可逆波,分别为0.69、0.94、1.42和1.70V(相对于SSCE),- [(Ru2Fe2II)-Fe-II](4+)可逆箭头[(Ru2FeFe)-Fe-II-Fe-II(III)](5+)可逆箭头[(Ru2Fe2III)-Fe-II]的电子氧化还原过程(6+)可逆箭头[(RuRuFe2III)-Ru-II-Fe-III](7+)可逆箭头[(RuRu2Fe2III)-Fe-III](8+)。电化学生成的[(Ru2FeFeIII)-Fe-II-Fe-II](5+)和[(Ru2Fe2III)-Fe-II](6+)在2350 nm处显示新的吸收带(ε= 5500m(-1)cm( -1))和1560 nm(ε= 10500 m(-1)cm(-1)),分别分配给从Fell到Fe-III以及从Ru-II到Fe的分子内IT(间隔转移)谱带-III离子。电子相互作用矩阵元素(H-AB)和电子离域度(alpha(2))估计为[(Ru2FeFe2III)-Fe-II-Fe-II](1090 cm(-1)和0.065 5+)状态,[(Ru2Fe2III)-Fe-II](6+)状态为1990 cm(-1)和0.065。 [参考:44]

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