Transient absorption and resonance raman investigations on the axial ligand photodissociation of halochromium(III) tetraphenylporphyrin

The axial ligand photodissociation processes of halochromium(III) tetraphen ylporphyrin ((XCrTPP)-T-III, X = Cl, Br) have been investigated in noncoord inating and coordinating solvents by transient Raman and absorption spectro scopic techniques. In noncoordinating solvents such as benzene, the upshift of the nu(2) and nu(4) hands and the disappearance of Cr-X stretching mode in the transient Raman spectra demonstrate the core size reduction of the porphyrin macrocycle accompanied by the photodissociation of axial halogen ligand atoms in the excited state. In coordinating solvents such as tetrahy drofuran (THF), where the solvent molecule is already attached to (XCrTPP)- T-III as an axial ligand to form (XCrTPP)-T-III(THF), the transient spectro scopic data indicate that the axial halogen ligand atoms photodissociate to form the Five-coordinate (CrTPP)-T-III(THF) on photoexcitation. The tempor al evolutions of photoinduced absorption and bleaching signals of (XCrTPP)- T-III in benzene exhibit biphasic decay profiles with time constants of 1 a nd 20 ms. The shorter decay is likely due to the four-coordinate photoexcit ed (CrTPP)-T-III* species, and the relatively slow decay component seems to be the recombination process returning to the original five-coordinate (XC rTPP)-T-III species. On the other hand, a significant reduction in the life time of photoexcited (ClCrTPP)-T-III in THF was observed as compared with t hat in benzene. This behavior seems to be caused by the excited five-coordi nate (CrTPP)-T-III(THF)* species, which decays rapidly with a time constant of 632 ps due to the participation of low-energy states in the deactivatio n process below the normally emissive tripmultiplet (pi,pi*) states. The el ectronic nature of the lowest excited state of the five-coordinate (CrTPP)- T-III(THF)* species is suggested to possess (pi,d(pi)) charge transfer char acter based on the comparison of transient Raman and absorption spectral fe atures with those of other paramagnetic metalloporphyrins. We explain the a xial ligand photodissociation processes in terms of the electron density ch ange in metal d orbitals, which is particularly sensitive to the interactio n with sigma-donor axial ligands.