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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.

dalton transactions

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

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