Tuning the Spin States of Two Apical Iron(II) Ions in a Pentanuclear Iron(II) Cluster Helicate through the Choice of Anions

摘要

Spin-crossover clusters with iron(II) high nuclearity are rare. By using 3,5-bis(pyridin-2-yl)-1,2,4-triazole (bptH) as the ligand with two bidentate chelating sites, we successfully obtained three pentanuclear iron(II) cluster helicate compounds [{FeII(μ-bpt)3}2FeII3(μ3-O)][FeII2(μ-Br)(μ-bpt)(NCS)4(H2O)]·2H2O·C2H5OH (1), [{FeII(μ-bpt)3}2FeII3(μ3-O)][FeII2(μ-bpt)2(NCS)4] (2), and [{FeII(μ-bpt)3}2FeII3(μ3-O)]I2·2C2H5OH (3). Research on single-crystal structure and magnetism has indicated that tuning the spin state of two iron(II) ions in axial direction is successfully realized by regulating the different counter anions: one apical [FeII(bpt)3]− unit exhibits spin-crossover behavior while the other [FeII(bpt)3]− unit remains in low spin state in 1, both apical ions are of high spin states in 2, and are of low spin states in 3.