Abstract
Copper β-substituted 5,10,15,20-tetraphenylporphyrins (CuTPP-β) and their cation radicals with varied electron-withdrawing/donating substituents were studied by resonance Raman spectroscopy. A1g, Eu and substituent modes were observed with Soret excitation. Q-band spectra and CuTPP-d7-CHO shifts aided mode assignments. In the cations, a2u is indicated as the highest occupied molecular, although an a1u CuTPP-OCH3 HOMO is predicted. Examination of the absorption spectra reveals orbital switching may occur for the neutral but not for the cationic species.
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