Vibrational probes and determinants of the S = 0 ⇌ S = 2 spin crossover in five-coordinate [Fe(TPP)(CN)]-.
Vibrational probes and determinants of the S = 0 ⇌ S = 2 spin crossover in five-coordinate [Fe(TPP)(CN)]-.
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s = 0 s = 2的振动探针和决定因素在五坐标[fe（tpp）（cn）]中的自旋跨界。
DOI：
10.1021/ic301719v
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发表时间：
2012-11-05
影响因子：
4.6
通讯作者：
Scheidt WR
中科院分区：
文献类型：
--
作者：
Li J;Peng Q;Barabanschikov A;Pavlik JW;Alp EE;Sturhahn W;Zhao J;Sage JT;Scheidt WR
本文报道了五配位氰基四苯基卟啉合铁（II）[Fe（TPP）（CN）]−的低频振动特性。核共振振动光谱已被用来测量所有涉及铁在几个温度下的低频振动;这产生了低自旋（S = 0）和高自旋（S = 2）状态的振动光谱。多温度取向的单晶测量有利于所有模式的振动特性的分配，并与DFT预测的光谱是一致的。整个铁振动光谱的可用性允许两个自旋状态之间的模式的完全相关性。这些数据表明，不仅这样做的振动频率转移到较低的值为高自旋的物种将预期由于在高自旋状态的较弱的键，但铁模式与配体模式的混合变化很大。给出了各模式的变化特征及其相互关系的示意图。降低的铁配体频率是负责自旋交叉的高自旋态的熵稳定的主要因素。
The low-frequency vibrational characterization of the spin crossover complex, five-coordinate cyano(tetraphenylporpyrinato)iron(II), [Fe(TPP)(CN)]−, is reported. Nuclear resonance vibrational spectroscopy has been used to measure all low-frequency vibrations involving iron at several temperatures; this yields vibrational spectra of both the low- (S = 0) and high-spin (S = 2) states. Multi-temperature oriented single-crystal measurements facilitate assignments of the vibrational character of all modes and are consistent with the DFT-predicted spectra. The availability of the entire iron vibrational spectrum allows for the complete correlation of the modes between the two spin states. These data demonstrate that not only do the frequencies of the vibrations shift to lower values for the high-spin species as would be expected owing to the weaker bonds in the high-spin state but that the mixing of iron modes with ligand modes changes substantially. Diagrams illustrating the changing character of the modes and their correlation is given. The reduced iron-ligand frequencies are the primary factor in the entropic stabilization of the high-spin state responsible for the spin crossover.
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影响因子：
3.3
作者：
Karunakaran, Venugopal;Benabbas, Abdelkrim;Champion, Paul M.
通讯作者：
Champion, Paul M.
影响因子：
16.6
作者：
Ikezaki, Akira;Takahashi, Masashi;Nakamura, Mikio
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Nakamura, Mikio
影响因子：
2.3
作者：
Ohgo, Y;Ikeue, T;Nakamura, M
通讯作者：
Nakamura, M
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
15
作者：
HOFFMAN, AB;HOARD, JL;COLLINS, DM
通讯作者：
COLLINS, DM