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|標題:||Highly conjugated multiporphyrins: synthesis, spectroscopic and electrochemical properties||作者:||Huang, T.H.
|關鍵字:||photoinduced electron-transfer;excited-state energy;porphyrin;oligomers;charge separation;epr spectroscopy;oxidation-states;building-blocks;arrays;dimers;coordination||Project:||Dalton Transactions||期刊/報告no：:||Dalton Transactions, Issue 18, Page(s) 2207-2213.||摘要:||
A series of meso-to-meso ethynyl-bridged multiporphyrin arrays have been synthesized using Sonogoshira palladium-catalyzed cross-coupling reactions involving the appropriate ethynylporphyrin and iodoporphyrin precursors. The absorption spectra of these multiporphyrins show splitting of the Soret bands and significant red shifts of the Q bands as compared to the combination of the corresponding components. These conjugated multiporphyrins also show red shifts in their emission spectra as the pi-conjugation is expanded. In the electrochemical measurements, the porphyrins dimer 7 shows two 1-e(-) oxidations at E-1/2 =+ 0.63 and + 0.76 V for the first electron abstraction from the two porphyrin rings, indicating electronic communication between the two porphyrin units. The porphyrin trimer 4 exhibits the first and second 1-e(-) oxidations at E-1/2 =+ 0.68 and + 0.77 V, respectively, which correspond to the two outer porphyrins. The cyclic voltammogram of pentamer 5 shows two overlapping 1-e(-) couples at E-1/2 =+ 0.56 and + 0.66 V, and one 2-e(-) couple at E-1/2 =+ 0.86 V, for the four outer porphyrin units. These results demonstrate that in the porphyrin trimer and pentamer the individual peripheral porphyrin units are electrochemically coupled via a central porphyrin core. The UV-Vis-NIR spectra of the oxidized species of these multiporphyrins exhibit a broad intervalence charge transfer (IVCT) band in the region from 1200 to 3000 nm. The present work shows that a central porphyrin unit appended with ethynyl bridges affords strong electronic interactions between the peripheral porphyrin rings over a distance of about 15 angstrom.
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