Substituent effect of the coordinated pyridine in a series of pyrazolato bridged dinuclear diiron(II) complexes on the spin-crossover behavior.

Two series of pyrazolato bridged dinuclear NCS and NCBH3 diiron(II) complexes with various types of 3- or 4-substituted pyridines, [{Fe(NCS or NCBH3)(X-py)}2(mu-bpypz)2], were prepared and their variable-temperature magnetic susceptibilities were measured. There were found linear correlations of the spin-crossover temperatures Tc not only between the NCS and NCBH3 complexes with the corresponding substituted pyridines, but also between the Tc and the Hammett constants, supporting the electronic substituent effect of the coordinated pyridine rather than a steric effect. The ligand field and the interelectronic repulsion parameters together with the thermodynamic data and/or cooperativity factor were discussed in relation with their spin-crossover behavior.