Femtosecond-Resolved Excited State Relaxation Dynamics of Copper(II) Tetraphenylporphyrin (CuTPP) After Soret Band Excitation

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Excited state relaxation dynamics of Copper (II) tetraphenylporphyrin (CuTPP) after Soret band excitation have been investigated in various solvents by femtosecond broadband transient absorption spectroscopy. Significant role of charge transfer state has been confirmed from fast relaxation of triplet CuTPP in pyridine, giving tau similar to 26.5 ps. In piperidine, the transient measured at 480 nm shows biexponential behavior with distinct time constants of 300 fs and 27.4 ps. The fast component with tau similar to 300 fs is attributed to relaxation of the CuTPP-piperidine adduct populated in the ground state, giving the intrinsic relaxation rate of the CuTPP exciplex for the first time. For CuTPP in O-coordinating solvents of 1,4-dioxane and tetrahydrofuran (THF), a completely new relaxation channel via the (2)[d(z2), d(x2-y2)] state is opened. As the exciplex formation is diffusion controlled, triplet CuTPP lifetimes in pure solvents employed here are all measured to be more or less same to give similar to 30 ps, whereas the (2)[d(z2), d(x2-y2)] exciplex formed by the ligation with O-coordinating solvents is found to relax much slowly to the ground state, giving lifetimes of similar to 360 and similar to 270 ps in 1,4-dioxane and THF, respectively.
Publisher
NATURE PUBLISHING GROUP
Issue Date
2017-12
Language
English
Article Type
Article
Keywords

TRANSIENT ABSORPTION-SPECTROSCOPY; FREE-BASE TETRAPHENYLPORPHYRIN; REACTION CENTER COMPLEX; SENSITIZED SOLAR-CELLS; FLUORESCENCE UP-CONVERSION; VIBRATIONAL-RELAXATION; CONDENSED-PHASE; ULTRAFAST DYNAMICS; ELECTRON-TRANSFER; ENERGY-TRANSFER

Citation

SCIENTIFIC REPORTS, v.7, no.16865

ISSN
2045-2322
DOI
10.1038/s41598-017-17296-z
URI
http://hdl.handle.net/10203/237688
Appears in Collection
CH-Journal Papers(저널논문)
Files in This Item
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