Issue 13, 2024

Impact of flexible hexyl chain ordering in a mononuclear spin crossover iron(iii) complex

Abstract

A novel FeIII complex [Fe(Hex-tnal)2]BPh4 (1) with a tridentate N2O ligand having an n-hexyl chain, Hex-Htnal (=1-((((1-hexyl-1H-1,2,3-triazol-4-yl)methyl)imino)methyl)naphthalen-2-ol), is reported. Temperature-dependent magnetic susceptibility measurements revealed that 1 exhibits a two-step spin crossover (SCO) transition in the 400–10 K temperature range, including an unusual gradual χMT change above RT (300–345 K) and a hysteretic χMT jump in a narrow temperature range of 345–357 K. These behaviors were also characterized by differential scanning calorimetry. Variable-temperature single-crystal X-ray diffraction studies revealed that the order–disorder transition and conformational change of the hexyl chains and the symmetry change associated with the re-entrant structural phase transition, namely triclinic P[1 with combining macron] (100–275 K) ↔ monoclinic C2/c (296–340 K) ↔ triclinic P[1 with combining macron] (360 K), are coupled to variations in intermolecular interactions and the N4O2 coordination environment, resulting in the occurrence of the unusual two-step SCO transition of 1. This study demonstrates that the flexible motion of alkyl substituents in the supramolecular lattice influences the occurrence of anomalous magnetic switching properties.

Graphical abstract: Impact of flexible hexyl chain ordering in a mononuclear spin crossover iron(iii) complex

Supplementary files

Article information

Article type
Paper
Submitted
14 2 2024
Accepted
28 2 2024
First published
01 3 2024

Dalton Trans., 2024,53, 5851-5860

Impact of flexible hexyl chain ordering in a mononuclear spin crossover iron(III) complex

H. Hagiwara and K. Sonoda, Dalton Trans., 2024, 53, 5851 DOI: 10.1039/D4DT00425F

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