Origin of the Broken Conjugation in <i>m</i>-Phenylene Linked Conjugated Polymers

Abstract

A quantum-chemical study of conformations and electronic structures of poly( m -phenylene) [PMP] and the related polyphenylenes was performed to elucidate the origin of the broken conjugation found in m -phenylene linked conjugated polymers. Potential energy curves of the polymers as a function of both torsion and helical angles were constructed through semiempirical Hartree−Fock band calculations at the Austin model 1 (AM1) level. It is found that two helical conformations of PMP are possible: one with a helical angle (α) of 72° and the other with α = 144°. The former is identical with the conformation of an oligomer in the solid state, m -deciphenyl structure. Our calculations predict that both helices are more stable by 2.5 kcal/mol per phenyl ring than the anti-coplanar conformation and that they exhibit absorption peaks at 5.8 eV. The electronic structure of PMP is, however, not affected significantly by increasing the planarity of a PMP chain but affected by copolymerization with other conjugated units. This implies that localization occurs in the m -phenylene ring itself. We examined the electronic structures of PMP and the related copolymers and found that the weak conjugation along the m -phenylene linked conjugated backbone is related to the inherent nodal nature of the frontier molecular orbitals of the unit even in the planar conformation.