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Updated: Feb 26, 2026
Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
A Series of Linear {FeIII2 FeII } Complexes with Paramagnetic Building-Block-Modified Spin Crossover Behaviors
Ji-Xiang Hu1, Yin-Shan Meng1, Liang Zhao1
1State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Rd., 116024, Dalian, P.R. China.
Abstract:
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 FeIII 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 FeII SCO unit and FeIII 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 FeII ion. The Tp* ligand showing the largest steric hindrance induces elongated FeII -N bond lengths and bending of the C≡N-FeII 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.
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