A theoretical study on electronic spectra of a novel series of metal substituted boron subphthalocyanine chloride

Boron subphthalocyanine chloride has been extensively studied by experimentalists and computational chemists due to its unique optical and electronic properties. It has been practical to modify the optical and physical properties of subphthalocyanine through axial, peripheral, and center substitutions or ring expansion. However, there have been few investigations on the substitution of central boron atom. In the present work, a new metal-substituted (center substitution of boron atom) series of boron subphthalocyanine chloride (metal = Fe, Co, Ni, Cu, and Zn) are theoretically designed utilizing modern density functional theory. The optimized results of this series in gas phase and with polarizable continuum model show that they may be chemically stable, and the predicted order of the stability of MSubPC is Fe>Cu>Ni>Co>Zn. Also, this new series of MSubPC molecules all becomes more non-planar and has much smaller dipole moments, which imply that they may be feasible for blend with organic acceptors. The HOMO-LUMO energy gaps of MSubPC (M=Co, Ni, Cu) are smaller than that of subPC. Furthermore, the wavelength of simulated absorption peaks of ZnSubPC and NiSubPC is red-shifted with respect to prototype subPC molecule in the visible region, and FeSubPC has noticeably stronger absorption strength than subPC because its excitation involves more orbital transitions and d electrons. The work here shows a new way to design photoelectric materials based on subphthalocyanine with center metal substitution. (c) 2019 Elsevier B.V. All rights reserved.