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- 저자 : Bolligarla, Ramababu (검색결과 1 건)
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Bolligarla, Ramababu,Ishida, Masatoshi,Shetti, Vijayendra S.,Yamasumi, Kazuhisa,Furuta, Hiroyuki,Lee, Chang-Hee The Royal Society of Chemistry 2015 Physical chemistry chemical physics Vol.17 No.14
<P>The synthesis, characterization, and photophysical and electrochemical properties of a novel tetrathiafulvalene (TTF)-annulated core-modified porphyrin (<B>1</B>) and its expanded rubyrin analogue (<B>2</B>) are described. The sulfur core modifications in <B>1</B> and <B>2</B> allow a feasible intramolecular charge transfer from the TTF fragments to the central conjugated core as inferred from comparative spectroscopic and electrochemical measurements. DFT calculations also support the intramolecular charge transfer nature of <B>1</B> and <B>2</B> upon excitation. Further the electronic perturbation of the TTF-annulated porphyrins was achieved by protonation, giving rise to a drastic change in the optical features with an extremely low energy band in the NIR region. The pronounced electron accepting ability of the macrocyclic core of the dicationic species (<B>H<SUB>2</SUB>1<SUP>2+</SUP></B> and <B>H<SUB>2</SUB>2<SUP>2+</SUP></B>) resulted in the thermally excited electron transfer occurring at room temperature as elucidated by EPR spectroscopy.</P> <P>Graphic Abstract</P><P>The effect of the core modification and protonation on the intramolecular charge transfer phenomenon was studied in the core-modified families of TTF-annulated porphyrinoids. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c4cp05385k'> </P>
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