Vacuum-evaporable spin-crossover complexes: physicochemical properties in the crystalline bulk and in thin films deposited from the gas phase

Four analogues of the spin-crossover complex [Fe(H(2)Bpz(2))(2)(phen)] (H(2)Bpz(2) = dihydrobis(pyrazolyl)borate; 2) containing functionalized 1,10-phenanthroline (phen) ligands have been prepared; i.e., [Fe(H(2)Bpz(2))(2)(L)], L = 4-methyl-1,10-phenanthroline (3), 5-chloro-1,10-phenanthroline (4), 4,7-dichloro-1,10-phenanthroline (5), and 4,7-dimethyl-1,10-phenanthroline (6). The systems are investigated by magnetic susceptibility measurements and a range of spectroscopies in the solid state and in thin films obtained by physical vapour deposition (PVD). Thermal as well as light-induced SCO behaviour is observed for 3-6 in the films. By contrast, thermal SCO in the solid state occurs only for 3 and 4 but is absent for 5 and 6. These findings are discussed in the light of cooperative and intermolecular interactions.