Issue 37, 2021

Auxiliary alkyl chain modulated spin crossover behaviour of [Fe(H2Bpz2)2(Cn-bipy)] complexes

Abstract

Three new alkyl chain substituted complexes [Fe(H2Bpz2)2(Cn-bipy)] (pz = pyrazolyl, Cn-bipy = bipyridine alkyl chain diester, n = 3 (3), 4 (4) and 5 (5)) show versatile spin state switching behaviour with different “tail” lengths as revealed by structural and magnetic analyses. The most striking phenomenon is observed for 5 which undergoes an abrupt spin transition accompanied by thermal hysteresis of ca. 10 K, which is attributed to crystal packing effects derived from the competition between π⋯π and C–H⋯O interactions. Interestingly, each of the complexes exhibits similar gradual and complete spin crossover in methanol solution with a transition temperature around 249 K, as deduced from temperature-dependent UV-vis spectroscopy. This highlights the differences between the solid state (ligand field; crystal packing) and solution (ligand field; solvation) effects on spin crossover. This work demonstrates that the length of the complex's alkyl chain substituents on the complex can have a large impact on the transition temperature and profile of solid state spin crossover, offering a potential path to the fabrication of soft matter spin crossover materials.

Graphical abstract: Auxiliary alkyl chain modulated spin crossover behaviour of [Fe(H2Bpz2)2(Cn-bipy)] complexes

Supplementary files

Article information

Article type
Paper
Submitted
01 6 2021
Accepted
01 7 2021
First published
26 7 2021

Dalton Trans., 2021,50, 12835-12842

Auxiliary alkyl chain modulated spin crossover behaviour of [Fe(H2Bpz2)2(Cn-bipy)] complexes

Y. Guo, A. Rotaru, H. Müller-Bunz, G. G. Morgan, S. Zhang, S. Xue and Y. Garcia, Dalton Trans., 2021, 50, 12835 DOI: 10.1039/D1DT01787J

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