Structure-function correlations in mononuclear manganese(iii) spin crossover systems with a big conjugated hexadentate Schiff-base ligand

Sheng Ze Zhao, Chun Yan Qin, Shi Wang, Masahiro Yamashita, Yong Hua Li, Wei Huang

Research output: Contribution to journalArticle

Abstract

This paper reports the syntheses, crystal structures and magnetic properties of spin crossover (SCO) salts of formulae [Mn(naphth-sal-N-1,5,8,12)]SbF6 (1), [Mn(naphth-sal-N-1,5,8,12)]AsF6 (2), [Mn(naphth-sal-N-1,5,8,12)]PF6·1/2CH3OH (3) and [Mn(naphth-sal-N-1,5,8,12)]ClO4 (4), where (naphth-sal-N-1,5,8,12)2- (2,2′-((1E,14E)-2,6,10,14-tetraazapentadeca-1,14-diene-1,15-diyl)diphenolate) is a big conjugated hexadentate Schiff-base ligand. Magnetic susceptibility measurements demonstrated that complexes 1 and 2 showed a gradual one-step SCO between the high-spin (HS, S = 2) and low-spin (LS, S = 1) states without thermal hysteresis. The transition temperatures T1/2 of the SbF6 (1) and AsF6 (2) salts estimated from the magnetic susceptibility measurements are 164 and 171 K, respectively. The existence of the crystal solvent of complex 3 changes the supramolecular packing, leading to close π⋯π stacking interactions between the phenyl groups of the ligands. These close stacking interactions hinder the flexibility of the whole ligand, precluding the spin transformation of complex 3 and leading to its stabilization in the HS state in the temperature range of 2-300 K. For 4, crystal structure analysis indicates that the reduction in the anion size leads to close contacts between the naphthalene rings. These C-H⋯π interactions provide a means for preventing the spin crossover occurring at low temperatures.

Original languageEnglish
Pages (from-to)4293-4305
Number of pages13
JournalDalton Transactions
Volume49
Issue number14
DOIs
Publication statusPublished - 2020 Apr 14

ASJC Scopus subject areas

  • Inorganic Chemistry

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