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Electronic and Steric Control of the Spin-Crossover Behavior in [(CpR)2Mn] Manganocenes
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-12-28 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02592
Jordi Cirera 1 , Eliseo Ruiz 1
Affiliation  

A computational study of the spin-crossover behavior in the family [(CpR)2Mn] (R = Me, iPr, tBu) is presented. Using the OPBE functional, the different electronic and steric effects over the metal’s ligand field are studied, and trends in the spin-crossover-temperature (T1/2) behavior are presented in terms of the cyclopentadienyl (Cp) ligand functionalization. Our calculations outlined a delicate balance between both electronic and steric effects. While an increase in the number of electron-donating groups increases the spin-crossover temperature (T1/2) to the point that the transition is suppressed and only the low-spin state is observed, steric effects play an opposite role, increasing the distance between the Cp rings, which in turns shifts T1/2 to lower values, eventually stabilizing the high-spin state. Both effects can be rationalized by exploring the electronic structure of such systems in terms of the relevant d-based molecular orbitals.

中文翻译:

[(Cp R2 Mn]锰合金自旋交叉行为的电子和立体控制

提出了对[[Cp R2 Mn](R = Me,i Pr,t Bu)族中自旋交叉行为的计算研究。使用OPBE官能团,研究了金属配体场上的不同电子和空间效应,并根据环戊二烯基(Cp)配体官能化提出了自旋交叉温度(T 1/2)行为的趋势。我们的计算概述了电子效果和空间效果之间的微妙平衡。给电子基团数量的增加会增加自旋交叉温度(T 1/2)到抑制转变并仅观察到低旋转状态的程度,空间效应起相反的作用,增加了Cp环之间的距离,进而将T 1/2移至较低的值,最终稳定了高的旋转状态。可以通过根据相关的基于d的分子轨道探索此类系统的电子结构来合理化这两种效应。
更新日期:2017-12-28
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