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Cooperativity in spin crossover materials as ligand's responsibility – investigations of the Fe(II) – 1,3-bis((1H-tetrazol-1-yl)methyl)bicyclo[1.1.1]pentane system

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Abstract

Criteria for a technologically relevant spin crossover (SCO) material include temperature and abruptness. A series of Fe(II) – 1,3-bis((1H-tetrazol-1-yl)methyl)bicyclo[1.1.1]pentane SCO complexes with various anions (BF4, ClO4, and PF6) designed using a structure–property based concept is reported. All complexes feature abrupt SCO-behavior with T1/2 between 170 K and 187 K. These materials demonstrate that without stabilizing the effects of incorporated solvents or a hydrogen bond-network, the observed cooperativity during high-spin–low-spin transition is anion independent and originates only from the rigidity and internal strain of the propellane-moiety in the ligand. Spectroscopy and structural investigations of these materials are supported by quantum chemical calculations.

Graphical abstract: Cooperativity in spin crossover materials as ligand's responsibility – investigations of the Fe(ii) – 1,3-bis((1H-tetrazol-1-yl)methyl)bicyclo[1.1.1]pentane system

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Publication details

The article was received on 28 Feb 2018, accepted on 16 Mar 2018 and first published on 16 Mar 2018


Article type: Communication
DOI: 10.1039/C8DT00781K
Citation: Dalton Trans., 2018, Advance Article
  • Open access: Creative Commons BY-NC license
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    Cooperativity in spin crossover materials as ligand's responsibility – investigations of the Fe(II) – 1,3-bis((1H-tetrazol-1-yl)methyl)bicyclo[1.1.1]pentane system

    C. Knoll, D. Müller, M. Seifried, G. Giester, J. M. Welch, W. Artner, K. Hradil, M. Reissner and P. Weinberger, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT00781K

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