Tunable Electronic and Magnetic Properties of Boron/Nitrogen-Doped BzTMCp*TMBz/CpTMCp*TMCp Clusters and One-Dimensional Infinite Molecular Wires

We systematically studied the structural, electronic, and magnetic properties of B/N-doped BzTMCp*TMBz/CpTMCp*TMCp (Bz = C₆H₆; Cp = C₅H₅; Cp* = C_5–<i>x</i>D_<i>x</i>H₅; D = B, N; <i>x</i> = 1, 2; TM = V, Cr, Mn, Fe) sandwich clusters and their infinite molecular wires using first-principle calculations. It is found that the B/N-doped ligands do not degrade the linear stacked sandwich configurations compared with the pristine hydrocarbon ligand complexes. Different from the N-doped complexes, the B-doped ligands lead to more charge transfers from metal atoms, and such behavior allows for the enhanced structure stabilities and adds the advantage of electronic and magnetic properties manipulation. Moreover, the B-doped ligand makes the one-dimensional sandwich molecular wires conserve half metallic properties of the pristine molecular wires, undergo half metal–semiconductor transition, and vice versa. Thus, a novel strategy for efficient tailoring of the electronic and magnetic properties of metal–ligand sandwich complexes is presented