• Title/Summary/Keyword: Photoinduced electron transfer

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Photoinduced Electron Transfer Reactions of Aryl Benzyl Sulfides Promoted by 2,4,6-Triphenylpyrilium Tetrafluoroborate (TP+BF4-)

  • Memarian, Hamid Reza;Ira, Mohammadpoor Baltork;Bahrami, Kiumars
    • Bulletin of the Korean Chemical Society
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    • v.27 no.1
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    • pp.106-110
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    • 2006
  • Photocatalytic electron transfer reactions of aryl benzyl sulfides using 2,4,6 triphenylpyrilium tetrafluoroborate ($TP^+BF_4^-$) resulted in the oxidation of these sulfides to the corresponding sulfoxides and also in most cases in the C-S bond cleavage of them along with formation of aromatic aldehydes. In these reactions, the formation of sulfide radical cation has been proposed, which undergoes either oxidation to the corresponding sulfoxide or C-S bond cleavage to the formation of aromatic aldehydes. The further oxidation of sulfoxides to sulfones has not been observed. The influence of substrate structures on the reaction pathways as well as the role of $O_2$ in this respect is discussed.

Formation and Cycloreversion of 2-Silacyclobuta[2.3]cyclophances via Photoinduced Electron Transfer

  • Mizuno, Kazuhiko;Nakanishi, Kazuhisa;Otsuji, Yoshio;Hayamizu, Tomoo;Maeda, Hajime;Adachi, Tomohiro;Ishida, Akito;Takamuku, Setsuo
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.121-126
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    • 2003
  • Irradiation of an acetonitrile solution containing dimethylbis(4-vinylphenylmethyl)silane 1a in the presence of 9,10-dicyanoanthracene leads to formation of the intramolecular photocycloadduct, 2-sila-cyclobuta[2.3]cyclophane(2a). In contrast, prolonged irradiation gave insoluble polymeric material. The photocycloreversion of 2a occurs efficiently (quantum yields exceeds unity) by use of redox-type photosensitization in the presence of magnesium perchlorate. The transient absorption spectra generated by pulse radiolysis and gamma-radiolysis show that the radical cation species generated from 1a is different from that arising from 2a.

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Nanoscale Protein Chip based on Electrical Detection

  • Choi, Jeong-Woo
    • 한국생물공학회:학술대회논문집
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    • 2005.04a
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    • pp.18-18
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    • 2005
  • Photoinduced electron transport process in nature such as photoelectric conversion and long-range electron transfer in photosynthetic organisms are known to occur not only very efficiently but also unidirectionally through the functional groups of biomolecules. The basic principles in the development of new functional devices can be inspired from the biological systems such as molecular recognition, electron transfer chain, or photosynthetic reaction center. By mimicking the organization of the biological system, molecular electronic devices can be realized $artificially^{1)}$. The nano-fabrication technology of biomolecules was applied to the development of nano-protein chip for simultaneously analyzing many kinds of proteins as a rapid tool for proteome research. The results showed that the self-assembled protein layer had an influence on the sensitivity of the fabricated bio-surface to the target molecules, which would give us a way to fabricate the nano-protein chip with high sensitivity. The results implicate that the biosurface fabrication using self-assembled protein molecules could be successfully applied to the construction of nanoscale bio-photodiode and nano-protein chip based on electrical detection.

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Photoinduced Electron Tansfer of Microperoxidase-8

  • Su, Chien-Hua;Lin, Ren-Jay;Chang, I-Jy
    • Journal of Photoscience
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    • v.6 no.3
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    • pp.129-133
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    • 1999
  • Microperoxidase 8 (MP8) has been prepared by sequential hydrolysis of cytochrome C by pepsin and trypsin. This five-coordinated heme-octapetide fragment provides a uniques structure to evaluate the electronic coupling efficiency to the iron through axial position and porphyrin edge. At alkali pH, Ru(bpy)2(im)22+ is completely quenched in AcMP8Ru complex . Transient kinetics measurement showed the decay rate to be ~1 $\times$1012S-1. Ruthenium bipyridine complex with a carboxyl group substituted bipyridine has been prepared adn reacted with MR 8 to yield N-terminus bound RuMP8 complex. The luminescence decay rate has been measured as 1 $\times$109S-1. By using semiclassical electron transfer theory, we found the electron transfer efficiency through axial positioin of iron prophyrin is as good through prophyrin edge.

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Ultrafast Time-Resolved Laser Spectroscopic Studies of trans-Bis(ferrocene-carboxylato)(tetraphenyl-porphyrinato)tin(IV): Intramolecular Electron-Transfer Dynamics

  • Jang, Joon-Hee;Kim, Hee-Jung;Kim, Hee-Joon;Kim, Chul-Hoon;Joo, Tai-Ha;Cho, Dae-Won;Yoon, Min-Joong
    • Bulletin of the Korean Chemical Society
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    • v.28 no.11
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    • pp.1967-1972
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    • 2007
  • Photophysical properties of a newly-synthesized porphyrin derivative, trans-bis(ferrocene carboxylato)- (5,10,15,20-tetraphenylporphyrinato)tin(IV) [Sn(TPP)(FcCOO)2] were investigated by means of steady-state and fs-time resolved laser spectroscopic techniques, and compared with those of a standard molecule, trans-dichloro( 5,10,15,20-tetraphenyl-porphrinato)tin(IV) [Sn(TPP)Cl2]. The fluorescence spectrum of Sn(TPP)- (FcCOO)2 was observed to exhibit dual emission bands originating from the S2-state and the S1-state, which was greatly quenched as compared to those of Sn(TPP)Cl2. The fs-time resolved fluorescence and transient absorption spectroscopic measurements revealed that the fluorescence quenching is due to formation of the long-lived charge transfer state by intramolecular electron transfer from ferrocene to the S2-excited SnTPP in addition to the enhanced non-radiative deactivation processes.

Molecular Wire World Having Metal Complexes

  • Choi, Chang-Shik
    • Rapid Communication in Photoscience
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    • v.3 no.3
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    • pp.42-47
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    • 2014
  • Development of molecular and supramolecular systems showing efficient photoinduced energy or electron transfer are of current research interest due to their applications in various chemical and biological processes. Various polypyridine metal complexes including Ru(II), Ru(III), Os(II), Pt(II), Fe(II), Re(I), Ir(III) and so on as a metal center introduce for expanding some more understanding of molecular-scale photoelectronics. Their complexes are concisely classified by the types of relay ligands as follows; (a) metal-direct ligand-metal system; dinuclear or trinuclear systems, (b) metal-nonconjugated ligand-metal system and metal-nonconjugated ligand system having flexible/rigid ligand, (c) metal-conjugated ligand-metal system, and (d) conjugated ligand-metal-conjugated ligand system and metal-self assembly ligand-metal system. It is pointed out that the role played by the relay ligands is important in constructing the metal complexes.

The Recent Current of Fluorescent Polypyridine Compounds Having Photofuctionality

  • Choi, Chang-Shik
    • Rapid Communication in Photoscience
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    • v.5 no.2
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    • pp.21-26
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    • 2016
  • Many kinds of fluorescent polypyridine compounds including bpy and dppz derivatives are described in understanding the recent current of fluorescent materials having photofuctionality. Those polypyridine compounds have the photofunctionality such as the fluorescence recognition and/or photo-switching. Furthermore, those compounds are applicated for the construction of long ranged photoinduced electron/energy transfer system. Various fluorescent ${\pi}-conjugation$ systems connected by amide or imine bond as well as the simple fluorescent bpy derivatives are introduced in this review paper.

Comparison of Photocyclization Reactions of Fluoro- vs Nonfluoro-Substituted Polymethyleneoxy Donor Linked Phthalimides

  • Park, Hea Jung;Ryu, Young Ju;Kim, Kyung Mok;Yoon, Ung Chan;Kim, Eunae;Sohn, Youngku;Cho, Dae Won;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1108-1114
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    • 2013
  • Photochemical reactions of fluoro- vs. nonfluoro-substituted polymethylenoxy chain linked phthalimide were carried out to explore how electronegative fluorine atoms inside the donor chain influence photocyclization reaction efficiencies and to briefly determine the alkali metal binding properties of the photoproducts. The results of this study show that the fluorine-substituted donor chain linked phthalimide undergoes inefficient photocyclization via single electron transfer (SET)-induced excited state pathways to generate 14-membered cyclic amidol compared to nonfluoro-analog due to low electron donor ability of the terminal oxygen donor site. These results show that photoinduced intramolecular SET processes arising from ${\alpha}$-silyl ether electron donors to phthalimides are largely dependent on the kinds of substituents inside donor chain. Finally, a preliminary study with the cyclic amidols generated in this effort showed that they have weak alkali metal cation binding properties regardless of absence/presence of fluoro-substituents.

A New Unsymmetrical Zinc Phthalocyanine as Photosensitizers for Dye-sensitized Solar Cells

  • Zhang, Dan;Zhang, Xue-Jun;Zhang, Lei;Mao, Li-Jun
    • Bulletin of the Korean Chemical Society
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    • v.33 no.4
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    • pp.1225-1230
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    • 2012
  • A new unsymmetrical zinc phthalocyanine has been designed and synthesized based on the 'push-pull' and extended ${\pi}$-conjugation concept for the dye-sensitized solar cells. Three tert-butoxy groups, which act as electron releasing ('push'), enhance the solubility of phthalocyanine in common organic solvents and reduce the aggregation. Hydroxy substituted 9,10-anthraquinones act as electron acceptors ('pull') for the study of photoinduced electron transfer processes as well as grafting onto nanocrystalline $TiO_2$. The new unsymmetrical zinc phthalocyanine was fully characterized by FTIR, UV-vis, $^1H$ NMR, cyclic voltammetry and differential pulse voltammetry. The new sensitizer was tested in dye-sensitized solar cells, and gave a better performance.