Hard X-ray-Induced Valence Tautomeric Interconversion in Cobalt-o-Dioxolene Complexes.
Hard X-ray-Induced Valence Tautomeric Interconversion in Cobalt-o-Dioxolene Complexes.
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DOI：
10.1021/acs.jpclett.7b01794
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发表时间：
2017-09
期刊：
影响因子：
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通讯作者：
T. M. Francisco;W. Gee;H. Shepherd;M. Warren;D. Shultz;P. Raithby;C. Pinheiro
中科院分区：
文献类型：
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作者：
T. M. Francisco;W. Gee;H. Shepherd;M. Warren;D. Shultz;P. Raithby;C. Pinheiro
价态互变异构互变（VTI）是发生在金属配合物中的可逆过程，其中分子内金属-配体电子转移伴随着金属离子自旋状态的改变，产生两个可切换的电子状态（氧化还原异构体）。在此，我们描述了[Co（diox）2（4-CN-py）2]·苯配合物（1）（diox = 3，5-di-t-butylsemiquinonate（SQ·-）和/或3，5-di-t-butylcatecholate（Cat 2-）自由基; 4-CN-py = 4-cyano-pyridine）在30-100 K的低温单晶研究。我们首次证明了硬X射线可以诱导VTI，并且相互转换摩尔分数取决于强度和曝光时间。这反过来表明，X射线作为一种探针，可能会改变许多在低温下研究的结构的性质，从而改变它们的性质。我们的研究结果为VTI研究增添了新的视角，并可能对整个研究光响应复合物的社区产生重大兴趣。
Valence tautomeric interconversion (VTI) is a reversible process occurring in metal complexes in which an intramolecular metal-ligand electron transfer is accompanied by a change of metal ion spin state, creating two switchable electronic states (redox isomers). Herein, we describe the low-temperature, 30-100 K, single-crystal study of the [Co(diox)2(4-CN-py)2]·benzene complex (1) (diox = 3,5-di-t-butylsemiquinonate (SQ•-) and/or 3,5-di-t-butylcatecholate (Cat2-) radical; 4-CN-py = 4-cyano-pyridine) using hard synchrotron X-ray radiation with different intensities. We demonstrate for the first time that hard X-rays can induce VTI, and that the interconversion molar fraction is dependent on both intensity and exposure time. This in turn shows that X-rays, as a probe, might be altering the very nature of many structures under investigation at low temperatures, and consequently their properties. Our findings add new perspectives to VTI studies and might be of significant interest to the entire community investigating photoresponsive complexes.