SEMIEMPIRICAL INVESTIGATION OF CHARGE-TRANSFER INTERACTIONS IN RIGID DIMETHOXYNAPHTHALENE BRIDGE PYRIDINIUM SYSTEMS

Abstract

Semiempirical quantum chemical calculations on a series of related dimethoxynaphthalene-{polynorbornyl,-(n,σ-bonds)}-pyridine (DMN-n-Py) and dimethoxynaphthalene-{polynorbornyl,(n,σ-bonds)}-N-methylpyridinium (DMN-n-MePy+) compounds have been carried out to gain insight into their electronic spectroscopy and into factors affecting photoinduced electron transfer in these novel molecular systems. The experimental electronic absorption spectra are found to be well described using the CNDO/S method. Using a simple charge-shift model and outer-sphere electron-transfer theory to take into account solvent effects, a good correlation exists between experimental charge-transfer state energies and tho..