Excited-state conformational dynamics of nickel (II) porphyrins

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Abstract
Time-resolved Raman and absorption spectroscopies were used to characterize the vibrational frequencies and electronic structure of the *B1g excited state of nickel (II) octaethylporphyrin and nickel (II) protoporphyrin IX diemthyl ester in noncoordinating solvents. Spectroscopic evidence for structural relaxation processes within the initial *B1g excited state on picosecond time scales suggests structural interconversion. Multiple conformations are expected to exist in solution based on crystal structures and previous resonance Raman studies. Here we present calculations that support conformational interconversions. Structural dynamics may play a role in the complex mechanisms of many biological systems that involve metalloporphyrins.