Enhanced intersystem crossing due to long-range exchange interaction in copper(II) porphyrin-free base porphyrin dimers: HOMO and spacer dependence

Highlights: • We found a parallel relationship between the two correlation lines of ln Δkisc vs. number of bonds. • Effects of HOMO of the terminal chromophore appear as the intercept of the correlation lines. • Difference of HOMO of the terminal porphyrin does not affect the interaction within the bridge part. • An expression involving both HOMO and spacer dependence for EISC rate was derived. - Abstract: Photodynamics induced by long-range exchange interaction was studied in two series of copper(II) porphyrin – free base porphyrin dimers linked via an aromatic spacer: one has a2u orbital as HOMO in the porphyrin π-system and the other has a1u orbital. Dependence on the HOMO as well as that on the spacer is presented for enhanced intersystem crossing (EISC) occurring in the free base half due to long-range coupling with the copper unpaired electron. Semilogarithmic plots of EISC rates vs. number of bonds show a linear correlation in each series of dimers. It was found that the two correlation lines show the same slope but different intercepts. This clearly indicates that electronic communication within the linkage does not depend on the terminal chromophore, while the terminal π-system affects the magnitude of EISC rates. Separately, a general expression for EISC rate, involving coupling between the terminal and linkage, was derived theoretically