Effect of CF3COOH on Decay Mechanism of the Excited State of a Free-base-Porphyrin-Perylene-Diimide Array

Abstract

Abstract: The effects of CF₃COOH concentration on the decay mechanism of a photo-excited free-base-porphyrin-perylene-diimide molecular array(TrPP-MDPTCDI) were investigated with UV-visible absorption spectroscopy and fluorescence spectroscopy. The data revealed that, the molecular array gave off a characteristic emission from the protonated free-base porphyrin upon the photo-excitation of both porpyrin and perylene-diimide subuntits. Based on the electronic structure, the protonation allowed the [H₂²⁺TrPP^*-MDPTCDI] to be relatively stable in all the photo-excited species. As a result, the electron transfer from free-base-porpyrin to perylene-diimide, a predominate decay channel in the absence of CF₃COOH was effectively inhibited, and the [H₂²⁺TrPP^*-MDPTCDI] formed upon the excitation of protonated free-base porphyrin(λ=438 nm) relaxed directly to the ground state with fluorescence; while the [H₂²⁺TrPP^*-MDPTCDI] formed upon the excitation of perylene-diimide subunit (λ=491 nm) relaxed via a charge-separation mediate species to [H₂²⁺TrPP-MDPTCDI^*], which decayed with radiation of protonated free-base porpyrin; the latter course was accompanied with a low efficiency energy transfer from perylene-diimide to the protonated free-base porphyrin subunit.

Key words: Protonation, Molecular array, Charge transfer, Energy transfer, Excited states

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SUN Jing-Zhi, YANG Xin-Guo, LI Han-Ying, HUANG Ji, WANG Mang . Effect of CF₃COOH on Decay Mechanism of the Excited State of a Free-base-Porphyrin-Perylene-Diimide Array[J]. Chem. J. Chinese Universities, 2004, 25(9): 1698.

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Effect of CF₃COOH on Decay Mechanism of the Excited State of a Free-base-Porphyrin-Perylene-Diimide Array

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