• Title/Summary/Keyword: Electron acceptor

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Counter Ion Effect on Photoinduced Electron Transfer Reaction between Ruthenium Complexes

  • Sonoyama, Noriyuki;Kaizu, Youkoh
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.481-486
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    • 1995
  • Quenching experiments by photoinduced electron transfer between a charged donor and a neutral acceptor were carried out in acetonitrile, dichloromethane and mixed solvents of acetonitrile and dichloromethane. Tris(2, 2'-bipyridine) ruthenium(II) ($[Ru(bpy)_3]^{2+}$) which has 2+ charge and dicyanobis (2, 2'-bipyridine) ruthenium(II) ($Ru(bpy)_2(CN)_2$) which has no charge were used as electron donors, and a series of tris(${\beta}$-diketonato) ruthenium (III) was used as acceptor. In dichloromethane, $[Ru(bpy)_3]^{2+}$ and its counter ions ($ClO{_4}^-$) form ion pair. In the estimate of ${\Delta}G$ of electron transfer, the electrostatic potential between counter ions and product ion pair produced by electron transfer must be taken into account. A similar effect of counter ions was found in mixed solvents of 10, 30, 50, 70 and 90% acetonitrile ratio in volume. The effect of counter ion on ${\Delta}G$ became smaller with the increase in acetonitrile ratio. The result in mixed solvents suggests that $[Ru(bpy)_3]^{2+}$ and its counter ions form ion pair even in 90% acetonitrile solution.

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Tailoring the Excited-State Intramolecular Proton Transfer (ESIPT) Fluorescence of 2-(2'-Hydroxyphenyl)benzoxazole Derivatives

  • Seo, Jang-Won;Kim, Se-Hoon;Park, Sang-Hyuk;Park, Soo-Young
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1706-1710
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    • 2005
  • The excited-state intramolecular proton transfer (ESIPT) fluorescence in the 2-(2'-hydroxyphenyl)benzoxazole (HBO) derivatives with different electron donor and acceptor substituents was studied by spectroscopic and theoretical methods. Changes in the electronic transition, energy levels, and orbital diagrams of HBO analogues were investigated by the semi-empirical molecular orbital calculation and were correlated with the experimental spectral position of ESIPT keto emission. It was found that the presence of substituents, regardless of their nature, resulted in the red-shifted absorption relative to HBO. However, the spectral change of the ESIPT fluorescence was differently affected by the nature of substituent: hypsochromic shift with electron donor and bathochromic shift with electron acceptor.

Porous Organic-inorganic Hybrids for Removal of Amines

  • Cho, Sung-Youl;Kim, Na-Ri;Cao, Guozhong;Kim, Joong-Gon;Chung, Chan-Moon
    • Bulletin of the Korean Chemical Society
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    • v.27 no.3
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    • pp.399-402
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    • 2006
  • Porous organic-inorganic hybrids have been prepared from tetraethylorthosilicate (TEOS) and organosilane precursors by sol-gel method. Two organosilanes, 3-(2,4-dinitrophenylamino)propyltriethoxysilane (DNPTES) and N-[[(2-nitrophenyl)methoxy]carbonyl]-3-triethoxysilylpropylamine (NPTES) were used to incorporate electron-accepting (di)nitrophenyl groups into the hybrids. The hybrids were characterized by FT-IR spectroscopy and elemental analysis, and their pore characteristics were studied by nitrogen sorption porosimetry. Surface area of the hybrids ranged from 563 to 770 $m^2$/g, pore volume, 0.23-0.30 $cm^3$/g, and porosity, 35-41%. It was demonstrated by UV-vis spectroscopy that aniline, ethylenediamine, and 1-aminonaphthalene could be removed from their hexane solutions in the presence of the hybrid powders. The removal of amines is attributable to donor-acceptor interaction between the electron-donating amines and electron-accepting (di)nitrophenyl moiety.

Substituent Effect on Fluorescence and Photoisomerization of 1-(9-Anthryl)-2-(4-Pyridyl)ethenes

  • Shin, Eun-Ju;Lee, Sang-Ha
    • Bulletin of the Korean Chemical Society
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    • v.23 no.9
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    • pp.1309-1338
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    • 2002
  • The fluorescence and photoisomerization quantum yields of trans-1-(9-anthryl)-2-(4-pyridyl)ethene (t-4-APyE), 1-(10-methyl-9-anthryl)-2-(4-pyridyl)ethene (t-4-MeAPyE), and 1-(10-chloro-9-anthryl)-2-(4- pyridyl)ethene (t-4-ClAPyE) were measured in cyclohexane, acetonitrile, and methanol at room temperature.Polar solvents result in the drastic reduction of fluorescence quantum yield and increase of photoisomerization quantum yield for all three compounds. These results are probably due to the stabilization of intramolecular charge transfer (ICT) excited state in polar solvent. The higher contribution of ICT in the presence of more electron-donating methyl substituent, manifested by largest positive fluorescence solvatochromism, indicates that the pyridine ring acts as an electron acceptor. Protonation or methylation makes pyridine ring stronger electron acceptor and causes long-wavelength ground state charge transfer absorption band and complete quenching of fluorescence. The fluorescence from t-4-APyE derivatives can be switched off responding external stimuli viz. medium polarity, protonation, or methylation.

Noncovalently Linked Zinc Porphyrin-Ru(bpy)3 Dyad Assembled via Axial Coordination

  • Kim, Dol;Shin, Eun-Ju
    • Bulletin of the Korean Chemical Society
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    • v.24 no.10
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    • pp.1490-1494
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    • 2003
  • Noncovalently linked electron donor-acceptor dyad consisting of zinc tetratolylporphyrin and pyridine appended ruthenium trisbipyridine comlex was prepared, via axial coordination of pyridine moiety in ruthenium trisbipyridine complex on zinc tetratolylporphyrin. For the purpose of comparison, axial coordination of pyridine-appended 2,2'-bipyridine on zinc tetratolylporphyrin was also investigated. The Kvalues were detemined based on absorption of fluorescence studies. The fluorescence of zinc teratolylporphrin was efficiently quenched upon axial coordination of pyridine moiety, prbably due to the photoinduced electron transfer from zinc tetrtolylporphyrin to ruthenium trisbipyridine, supported by free enegy estimation.

Effect of Herbicide Paraquat on Electron Donor and Acceptor (제초제 Paraquat의 전자수용 및 방출에 대한 영향)

  • Kim Mi-Lim;Choi Kyung-Ho
    • Journal of Life Science
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    • v.15 no.2 s.69
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    • pp.311-315
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    • 2005
  • When paraquat was added to the bacterial membrane or mitochondrial suspension, the mixture turned dark blue, but the color was disappeared by aeration. The same phenomenon was seen when electrons were supplied to the paraquat. Blue color appeared from near the cathode, and then spreaded to whole transit system. Coloration was accelerated by addition of alkali, but the color was reduced by addition of acid or oxygen. Paraquat exhibited absorption at ultraviolet region by electron transfer at the concentrations as low as 1.0 mM which did not exert difficulty in showing color reaction. Paraquat caused the increase of the optical density at 340 nm by electron transit, and an aspect of that had a strong resemblance to NADH. The acute toxic action of paraquat seemes to depend on inhibition of energy metabolism cased by paraquat action of electron donor and acceptor.

Spectrophotometric Determination of Antihistaminics by using Iodine as Electron Acceptor (요오드를 전자수용체로 한 항히스타민제의 분광학적 분석)

  • Moon, Hong-Seob;Baik, Chai-Sun
    • YAKHAK HOEJI
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    • v.33 no.3
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    • pp.141-148
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    • 1989
  • The weak UV absorbing antihistaminics such as chlorpheniramine, triprolidine, tripelennamine and diphenhydramine were analyzed by charge-transfer spectrophotometric method. The results obtained are summarized as folows. It was possible to determine a weak UV absorbing antihistaminics using the intense charge-transfer UV bands in chloroform. Charge transfer complexes were formed in a 1:1 ratio between antihistaminics and iodine in chloroform. Linear relationship was found between absorbance and concentration in the range of $1.0\;{\times}\;10^{-5}M-5.0\;{\times}\;10^{-5}M$ for chlorpheniramine( ${\varepsilon}\;=\;2.082\;{\times}\;10^4$) and tripelennamine ( ${\varepsilon}\;=\;1.578\;{\times}\;10^4$), $1.0\;{\times}\;10^{-5}M-8.0\;{\times}\;10^{-5}M$ for triprolidine ( ${\varepsilon}\;=\;1.120\;{\times}\;10^4$) and $1.0\;{\times}\;10^{-5}M-1.0\;{\times}\;10^{-4}M$ for diphenhydramine ( ${\varepsilon}\;=\;9.900\;{\times}\;10^3$). Charge transfer complexes of chlorpheniramine, triprolidine and tripelennamine have absorption maxima at 293 nm and complex form of diphenhydramine has absorption maximum at 270 nm. By UV, IR spectra, it could be inferred that CT-complexes were formed by interaction between the basic nitrogen of antihistaminics as electron donor (non bonding electron) and iodine as electron acceptor (${\sigma}$ bonding electron).

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Isoindigo Based Small Molecules for High-Performance Solution-Processed Organic Photovoltaic Devices

  • Elsawy, W.;Lee, C.L.;Cho, S.;Oh, S.H.;Moon, S.H.;Elbarbary, A.;Lee, Jae-Suk
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.245.2-245.2
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    • 2013
  • Solution processed organic photovoltaic devices have relatively less attention compared to polymer photovoltaic devices even though they have high possibility to be developed because they have both advantages of polymer and organic, such as solution processable, no synthetic batch dependence of photovoltaic performance, high purity and high charge carrier mobility as well as relatively high efficiency (~7%). In addition, solution processed organic photovoltaic devices have an advantage of easiness to study the relationship between the molecular structure and photovoltaic performance due to its simple structure. In this work, five isoindigo based low band gap donor-acceptor-donor (D-A-D) small molecules with different electron donating strength were synthesized for investigating the relationship between the molecular structure and photovoltaic performance, especially, investigating the effects of different electron donating effect of donor group in isoindigo backbone to photovoltaic device performance. The variation of electron donating strength of donor group strongly affected the optical, thermal, electrochemical and photovoltaic device performances of isoindigo organic materials. The highest power conversion efficiency of ~3.2% was realized in bulk heterojuction photovoltaic device consisted of the ID3T as donor and PC70BM as acceptor. This work demonstrates the great potential of isoindigo moieties as electron deficient units as well as guideline for synthesis of donor-acceptor-donor (D-A-D) small molecules for realizing highly efficient solution processed organic photovoltaic devices.

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Synthesis and Characterization of Phenanthrene-substituted Fullerene Derivatives as Electron Acceptors for P3HT-based Polymer Solar Cells

  • Mi, Dongbo;Park, Jong Baek;Xu, Fei;Kim, Hee Un;Kim, Ji-Hoon;Hwang, Do-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1647-1653
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    • 2014
  • 9,10-Bis(bromomethyl)phenanthrene reacted with fullerenes via a Diels-Alder reaction to give phenanthrene-substituted fullerene mono-adducts (PCMA) and bis-adducts (PCBA) as electron acceptors for organic photovoltaic cells (OPVs). The syntheses of the fullerene derivatives were confirmed by $^1H$ $^{13}C$ NMR spectroscopy and MALDI-TOF mass spectrometry. PCMA and PCBA showed better light absorption in the UV-visible region than $PC_{61}BM$. Their electrochemical properties were measured using cyclic voltammetry. Accordingly, the lowest unoccupied molecular orbital (LUMO) energy levels of PCMA and PCBA were -3.66 and -3.57 eV, respectively. Photovoltaic cells were fabricated with a ITO/PEDOT:PSS/poly(3-hexylthiophene)(P3HT):acceptor/LiF/Al configuration, where P3HT and PCBA are the electron donors and acceptors, respectively. The polymer solar cell fabricated using the P3HT:PCBA active layer showed a maximum power conversion efficiency of 0.71%.