Ultrafast photodissociation of a metalloporphyrin in the condensed phase
Document Type
Article
Publication Title
The Journal of Chemical Physics
Abstract
The photodissociation of axial ligands from six-coordinate nickel (II) porphyrins in solution has been studied by transient absorption spectroscopy with subpicosecond resolution. Our observations indicate that the deligation process takes place during the first several picoseconds following optical excitation of the macrocycle as the initially observed 3(π,π*) state relaxes to a dissociative ligand field excited state. No evidence is found for geminate recombination of the two ejected ligands with the four-coordinate photoproduct. A small fraction of the complexes appear to loose only one ligand. The absorption bands of the initially observed excited state and of the deligated species are also found to undergo a spectral evolution within the first 10 ps similar to that uncovered recently in the photodynamics of four-coordinate nickel(II) porphyrins in noncoordinating solvents [J. Rodriguez and D. Holten, J. Chem. Phys. 91, 3525 (1989)]. Several possibilities are considered for these time-dependent spectral shifts, including vibrational dynamics. © 1990 American Institute of Physics.
First Page
5944
Last Page
5950
DOI
10.1063/1.458364
Publication Date
1-1-1990
Recommended Citation
Rodriguez, Juan and Holten, Dewey, "Ultrafast photodissociation of a metalloporphyrin in the condensed phase" (1990). Basic Sciences Faculty Publications. 211.
https://doi.org/10.1063/1.458364
https://collections.uhsp.edu/basic-sciences_pubs/211