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A Series of Linear {Fe III 2 Fe II } Complexes with Paramagnetic Building‐Block‐Modified Spin Crossover Behaviors
Author(s) -
Hu JiXiang,
Meng YinShan,
Zhao Liang,
Zhu HaiLang,
Liu Lei,
Liu Qiang,
Jiao ChengQi,
Liu Tao
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703110
Subject(s) - steric effects , paramagnetism , crystallography , octahedron , spin crossover , chemistry , ligand (biochemistry) , boron , stacking , ion , materials science , stereochemistry , crystal structure , condensed matter physics , physics , organic chemistry , biochemistry , receptor
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 π–π stacking interactions play a key role in the thermal hysteresis and anomalous octahedral distortion parameter Σ 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.