CNDO molecular orbital calculations on porphyrins - I. Ground and excited states of porphyrin, divinylporphyrin and tetraphenylporphyrin

Abstract Semi-empirical CNDO/2 MO calculations are reported for the ground states of porphyrin, 2,4-divinylporphyrin (DVP), and α,β,γ,δ-tetraphenylporphyrin (TPP). Results for TPP refer to the conformation with all phenyl groups perpendicular to the porphyrin ring, calculated to be 108 kJ mol −1 more stable than the coplanar conformation. The substituents withdraw electron density where they are attached to the porphyrin ring, increasing selected orbital energies. The vinyl groups also modify the electron population at nitrogen. CNDO/S calculations with extensive configuration interaction are reported for excited states. The lowest singlet states are closely similar in energy and composition for all three molecules, except for an extra state and more complex compositions in DVP above 3 eV. The lowest triplet states of porphyrin and DVP are very similar, while those of TPP are comparable in energy or composition but not both. Experimental data on the excited states are broadly consistent with the calculations, although comparisons for the excited triplets are tentative.