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六胺铁（II）配合物中的自旋交叉：计算预测的实验验证

Spin Crossover in a Hexaamineiron(II) Complex: Experimental Confirmation of a Computational Prediction.

作者信息

Bernhardt Paul V, Bilyj Jessica K, Brosius Victor, Chernyshov Dmitry, Deeth Robert J, Foscato Marco, Jensen Vidar R, Mertes Nicole, Riley Mark J, Törnroos Karl W

机构信息

School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, 4072, Australia.

European Synchrotron Radiation Facility, 71 Avenue des Martyrs, Grenoble, 38000, France.

出版信息

Chemistry. 2018 Apr 6;24(20):5082-5085. doi: 10.1002/chem.201705439. Epub 2018 Jan 29.

DOI:10.1002/chem.201705439
PMID:29315883
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5988046/
Abstract

UNLABELLED

Single crystal structural analysis of [Fe (tame) ]Cl ⋅MeOH (tame=1,1,1-tris(aminomethyl)ethane) as a function of temperature reveals a smooth crossover between a high temperature high-spin octahedral d state and a low temperature low-spin ground state without change of the symmetry of the crystal structure. The temperature at which the high and low spin states are present in equal proportions is T =140 K. Single crystal, variable-temperature optical spectroscopy of [Fe (tame) ]Cl ⋅MeOH is consistent with this change in electronic ground state. These experimental results confirm the spin activity predicted for [Fe (tame) ] during its de novo artificial evolution design as a spin-crossover complex [Chem. Inf.

MODEL

2015, 55, 1844], offering the first experimental validation of a functional transition-metal complex predicted by such in silico molecular design methods. Additional quantum chemical calculations offer, together with the crystal structure analysis, insight into the role of spin-passive structural components. A thermodynamic analysis based on an Ising-like mean field model (Slichter-Drickammer approximation) provides estimates of the enthalpy, entropy and cooperativity of the crossover between the high and low spin states.

摘要

未标记

对[Fe(tame)]Cl·MeOH（tame = 1,1,1 - 三（氨甲基）乙烷）随温度变化进行的单晶结构分析表明，在高温高自旋八面体d态和低温低自旋基态之间存在平滑转变，且晶体结构对称性不变。高自旋态和低自旋态以等比例存在时的温度为T = 140 K。[Fe(tame)]Cl·MeOH的变温单晶光谱与电子基态的这种变化一致。这些实验结果证实了[Fe(tame)]在其作为自旋交叉配合物的从头人工进化设计过程中预测的自旋活性[化学信息模型：2015, 55, 1844]，首次对通过此类计算机分子设计方法预测的功能性过渡金属配合物进行了实验验证。额外的量子化学计算与晶体结构分析一起，深入了解了自旋被动结构成分的作用。基于类伊辛平均场模型（Slichter - Drickammer近似）的热力学分析提供了高自旋态和低自旋态之间转变的焓、熵和协同性的估计值。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/47c809fc9561/CHEM-24-5082-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/0c6dc9a05772/CHEM-24-5082-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/a6c8ac25619d/CHEM-24-5082-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/b351746edfe4/CHEM-24-5082-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/57213431b083/CHEM-24-5082-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/8d251371d22f/CHEM-24-5082-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/47c809fc9561/CHEM-24-5082-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/0c6dc9a05772/CHEM-24-5082-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/a6c8ac25619d/CHEM-24-5082-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/b351746edfe4/CHEM-24-5082-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/57213431b083/CHEM-24-5082-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/8d251371d22f/CHEM-24-5082-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8319/5988046/47c809fc9561/CHEM-24-5082-g004.jpg

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