Electronic stark effect studies of a porphyrin-based push-pull chromophore displaying a large first hyperpolarizability: State-specific contributions to β

Electroabsorption or Stark effect spectroscopy has been applied to a pair of porphyrin-based chromophores with the aim of deriving a detailed understanding of the origin of the remarkable first hyperpolarizability, β, of one of the chromophores:  [5-[[4‘-(dimethylamino)phenyl]ethynyl]-15-[(4‘‘-nitrophenyl)ethynyl]-10,20-diphenylporphinato]zinc(II). The measurements show that significant changes in molecular dipole moment, Δμ, accompany excitations of x-polarized transitions of the aminophenyl (donor)/nitrophenyl (acceptor) functionalized chromophore, but are absent for a related chromophore lacking the donor and acceptor groups. For linear chromophores, changes in dipole moment are a prerequisite to effective molecular first hyperpolarization and incident light frequency doubling behavior. A more detailed consideration of the available |Δμ| data, within the context of a conventional two-level model, has yielded the following:  (a) specific information about the roles of each of seven electronic and vibron...