Abstract
Optical and time-resolved EPR(TREPR) studies were made on the excited states of fluorine-substituted magnesium tetraphenylporphines (MgF−TPPs) including related Mg porphyrins. From the analyses of TREPR spectra it was found that the zero-field splitting parameter, D, increased with an increasing number of substituents, e.g. fluorine atoms. This result is interpreted by the fact that 3(a2ueg) and 3(a1ueg) configurations are heavily mixed via vibronic couplings in the lowest excited triplet (T1) states of MgF−TPPs. Other T1 properties such as a T1 energy, a triplet lifetime, and an appearance of the b1g band in the phosphorescence supported the mixings. The mixings due to configuration interactions were studied in the lowest excited singlet (S1) states of MgF−TPPs by measuring absorption coefficients and intensities of vibronic bands both in the absorption and fluorescence. The magnitudes of the mixings were also evaluated in the S1 states of MgF−TPPs.
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