Abstract
The effect of axial ligand 4-N, N-dimethyl aminopyridine (DMAP) on the fluorescence property of the second singlet excited state (S2) and first singlet excited state (S1) of 5,10,15, 20-tetra (p-methoxyl) phenyl zinc porphyrin has been investigated using steady-state absorption, fluorescence spectroscopy and picosecond time-resolved fluorescence spectroscopy. Hot fluorescence is clearly observed and is then reasonably assigned to the higher vibronic level from S1 state. A further analysis of fluorescence kinetics results shows that the coordination of DMAP to the zinc ion results in a decrease of hot fluorescence lifetime and an increase of the relative content of hot fluorescence. Similar phenomenon was observed with respects to S1 fluorescence upon the addition of DMAP in toluene. For a complete understanding of such an effect, a possible mechanism has been put forward and discussed in detail.
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Scherer, P. J., Fischer, S. F., Quantum treatment of the optical spectra and the initial electron transfer process within the reaction center of Rhodopseudomonas viridis, Chem. Phys., 1989, 131(1): 115–127.
Luo, C. H., Research progress of actinotherophy sensitizer combined with azoles, Foreign Medical Section on Pharmacy, 1996, 23(3): 140–143.
Miller, J. R., Dorough, G. D., Pyridinate complexes of some metallo-derivatives of tetraphenylporphine and tetraphenylchlorin, J. Am. Chem. Soc, 1952, 74: 3977–3981.
Caldin, E. F., Field, J. P., Kinetics of complex formation between zinc meso-tetraphenylporphyrin and some nitrogen bases in aprotic solvents, studied by an improved microwave temperature-jump method, J. Chem. Soc, Faraday Trans. I, 1982, 78(6): 1923–1935.
Jean, B. K., John, J. L., Frederick, R. L., A mechanism study of the synthesis and spectral properties of meso-tetraarylporphyrins, J. Am. Chem. Soc, 1972, 94(11): 3986–3992.
Shelnutt, J. A., Electronic structure of metallourporphyrins andtheir π-π dimmers, J. Phys. Chem., 1984, 88(21): 4988–4992.
Elsaesser, T., Kaiser, W., Vibrational and vibronic relaxation of large polyatomic molecules in liquids, Annu. Rev. Phys. Chem., 1991,42: 83–107.
Iwata, K., Hamaguchi, H., Microscopic mechanism of solute-solvent energy dissipation probed by picosecond time-resolved Raman spectroscopy, J. Phys. Chem., A, 1997, 101(4): 632–637.
Fourkas, J. T., Kawashima, H., Nelson, A., Theory of nonlinear optical experiments with harmonic oscillators, J. Chem. Phys., 1995, 103(11): 4393–4406.
Mataga, N., Shibata, Y., Chosrowjan, H. et al., Internal conversion and vibronic relaxation from higher excited electronic state of porphyrins: femtosecond fluorescence dynamic studies, J. Phys. Chem., B, 2000, 104 (17): 4001–4004.
Collins, D. M., Hoard, J. L., The crystal structure and molecular stereochemistry of α, β, γ, δ-tetra(4-pyridyl) porphinatomonopydinezinc (II), An appraisal of bond strain in the porphine skeleton, J. Am. Chem. Soc., 1970, 92(12): 3761–3771.
Misono, Y., Linmantara, L., Koyama, Y. et al., Solvent effects on the resonance Raman and electronic absorption spectra ofbacteriorchlorophyll a cation radical, J. Phys. Chem., 1996, 100(6): 2422–2429.
Aaviksoo, J., Freiberg, A., Savikhin, S., Picosecond fluorescence study of the lifetimes of metalloporphyrin S1 and S2 states, Chem. Phys. Lett., 1984, 111(3): 275–278.
Englman, R., Jortner, J., The energy gap laws for radiationless transitions in large molecules, Mol. Phys., 1970, 18: 145–146.
Nagae, H., Kuki, M., Zhang, J. P. et al., Vibronic coupling through the in-phase C=C stretching mode plays a major role in the 2Ag − to lAg − internal conversion of all-trans-β-carotene, J. Phys. Chem., A, 2000, 104(18): 4155–4166.
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Juan, F., Huijuan, Z., Junfeng, X. et al. Influence of axial coordination on the photophysical property of excited state of zinc porphyrin. Sc. China Ser. B-Chem. 46, 137–143 (2003). https://doi.org/10.1360/03yb9020
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DOI: https://doi.org/10.1360/03yb9020