Vibration and Fluorescence Spectra of Porphyrin- CoredBis(methylol)-propionic Acid Dendrimers 英文参考文献.docVIP

Sensors 2009, 9, 1937-1966; doi:10.3390/OPEN ACCESS sensors ISSN 1424-8220 /journal/sensors Article Vibration and Fluorescence Spectra of Porphyrin-Cored 2,2-Bis(methylol)-propionic Acid Dendrimers Boris Minaev 1 and Mikael Lindgren 2,* 1 Department of Chemistry, Bogdan Hmelnitskij National University, 18031 Cherkassy, Ukraine; E-Mail: bfmin@rambler.ru 2 Department of Physics, Norwegian University of Science and Technology, 7491 Trondheim, Norway * Author to whom correspondence should be addressed; E-Mail: mikael.lindgren@ntnu.no; Tel.: +47-7359-3414; Fax: +47-7359-7710 Received: 21 October 2008; in revised version: 27 February 2009 / Accepted: 16 March 2009 / Published: 16 March 2009 Abstract: Bis-MPA dendron-coated free-base tetraphenylporphyrin and zinc-tetraphenyl- porphyrin (TPPH2 and TPPZn) were studied in comparison with simple porphyrins (H2P, ZnP) by theoretical simulation of their infrared, Raman and electronic absorption spectra, as well as fluorescense emission. Infrared and fluorescence spectra of the dendrimers were measured and interpreted along with time-resolved measurements of the fluorescence. The 0-1 emission band of the dendron substituted TPPZn was found to experience a heavy substitution-effect. The 0-1 vibronic emission signal is associated with a longer decay time (approx. 7 - 8 ns) than the 0-0 emission (approx. 1 - 1.5 ns). The former contributed with more relative emission yield for larger dendron substituents, in agreement with the appearance of steady-state emission spectra showing increased contribution from the 0-1 vibronic fluorescence band at 650 nm. No such substitution effect was observed in the electronic or vibrational spectra of the substituted free-base variant, TPPH2. Vibration spectra of the parent porphyrins (H2P, ZnP, TPPH2 and TPPZn) were calculated by density functional theory (DFT) using the B3LYP/6-31G** approximation and a detailed analysis