The effects of peripheral substitution of strongly electron-withdrawing groups (CN and F) on the electronic properties of Si(Pc)(OH)2(Pc = phthalocyaninato) are studied via the discrete-variational local exchange (DV-Xα) formalism. Comparisons are made to the electronic structure of the parent molecule, Si(Pc)(OH)2, and the results are discussed in terms of changes in the tight-binding band structure of the corresponding cofacially joined phthalocyaninato polymers. Transition-state calculations yield optical and photoemission spectral energy predictions. The former are in good agreement with experimental data. There is a pronounced lowering of all orbital energies and a substantial increase in ionization potential upon CN and F substitution.
ASJC Scopus subject areas
- Colloid and Surface Chemistry