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论文类型：期刊论文

发表时间：2017-11-13

发表刊物：CHEMISTRY-A EUROPEAN JOURNAL

收录刊物：SCIE、EI、PubMed

卷号：23

期号：63

页面范围：15930-15936

ISSN号：0947-6539

关键字：building blocks; light-induced spin crossover; spin crossover; stacking interactions; steric hindrance

摘要：Tuning of the spin crossover (SCO) behavior through paramagnetic building blocks with different steric hindrance effects is of great interest in terms of the synergy between SCO and magnetic interactions. Herein, the steric effect of specified Fe-III building blocks is modified, from the large Tp* (hydridotris(3,5-dimethylpyrazol-1-yl)borate) analogue to a small Tp (hydrotris(pyrazolyl)borate) derivative; the Fe-II SCO unit and Fe-III paramagnetic ions are incorporated into three well isolated trinuclear complexes featuring thermally induced and light-induced SCO properties. Reanalysis of the structures reveals that - stacking interactions play a key role in the thermal hysteresis and anomalous octahedral distortion parameter sigma around the Fe-II ion. The Tp* ligand showing the largest steric hindrance induces elongated Fe-II-N bond lengths and bending of the C  N-Fe-II angle in 1, as well as having a relatively large electron donor effect, which leads to the lowest thermal transition temperature among the three compounds.