The Paramagnetic or Spin Crossover Iron(III) Complexes Based-on Pentadentate Schiff Base Ligand: Crystal Structure, and Magnetic Property Investigation

A series of bi-or mononuclear hexacoordinate iron(III) complexes, [Fe(L)][Fe(bpb)(CN)2]& BULL;CH3OH & BULL;0.5H2O (1), [Fe(L)] [Co(bpb)(CN)2]& BULL;CH3OH (2) [(Fe (L))2(4,4'-bipy)](BPh4)2 (3), [Fe(L)(py)](BPh4) (4) and [Fe(L)(dmap)](BPh4) (5) (bpb = 1,2-bis(pyridine-2-carboxamido)benzenate, L = N,N'-bis(2-hydroxybenzyliden)-1,7-diamino-4-azaheptane, dmap = 4-dimethylaminopyridine), have been prepared with the pentadentate Schiff base iron(III) compound as assemble pre-cursor and characterized by element analysis, IR and X-ray diffraction. Single crystal structural determination revealed the neutral cyanide-bridged binuclear entity for complexes 1 and 2 and the cationic di-or mononuclear structure for complexes 3-5 with the positive charge(s) balanced by BPh4- ion(s). The experimental study and theoretical simulation of the magnetic property discovered the ferromagnetic coupling between the Fe(III) ions bridged by cyanide group in complex 1 and the always high spin state of the Fe(III) ion coordinated to the Schiff base ligand in both complexes 1 and 2. The temperature dependent magnetic susceptibility investigation over complexes 3-5 showed the occurrence of the thermo-induced gradual complete spin crossover (SCO) property at about 115, 170 and 200 K, respectively.