• Title/Summary/Keyword: photoinduced charge transfer

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Photoinduced Charge-Transfer Association of Tetracyanoquinodimethane with Aminobiphenyls

  • Kim, Yong-Hee;Jung, Sang-Don;Chung, Myung-Ae;Song, Ki-Dong;Cho, Dae-Won
    • Bulletin of the Korean Chemical Society
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    • v.29 no.5
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    • pp.948-952
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    • 2008
  • The molecular association of acceptors with electron donors is studied in the highly-polar solvent $CH_3CN$. Tetracyanoquinodimethane (TCNQ) forms a stable charge-transfer complex with donor molecules such as 4- aminobiphenyl (4-AB), benzidine (BD) and 2-aminobiphenyl (2-AB) with high association constants. The complexes of TCNQ with 4-AB or BD show new absorption bands at around 800 and 500 nm, which can be identified as reduced $TCNQ^{{\bullet}-}$ and $TCNQ^{2-}$ species, respectively. These bands grow quickly upon photoirradiation, implying that the charge-transfer complexes are easily formed in an excited state. Conversely, a small spectral manifestation of the charge transfer was observed in the case of 2-AB complex. It is demonstrated that the structural orientation between the geminate ion pairs could play an important role in building a stable complex.

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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Photoinduced Electron Transfer from Excited Ruthenium Complexes at Nanocrystalline $TiO_2$ Electrodes

  • 배종현;김동환;김영일;김강진
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.567-573
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    • 1997
  • Photoinduced electron transfer from the charge-transfer excited states of Ru(tpy)(bpy(COOH)₂)$CN^+$, Ru(tpy)(bpy(COOH)₂)$Cl^+$, Ru(tpy)(bpy(COOH)₂)H₂+O², and Ru(tpy)(bqu(COOH)₂)$Cl^+$ to the conduction band of TiO₂ has been studied through photoelectrochemical methods. Ru(tpy)(bpy(COOH)₂)$CN^+$ produced the highest current density and open-circuit photovoltage, whereas Ru(tpy)(bqy(COOH)₂)$Cl^+$ produced the lowest values. A potential barrier was employed to explain the experimental result that the rate of the electron transfer increases with increasing the energy difference between the donor and acceptor. A sensitizer with a high current density yielded a high photovoltage and a high conversion efficiency. The reduction rate of the oxidized sensitizer decreased with the increases in the reduction potential of the sensitizer, resulting in a poor stability of a photoelectrochemical cell.

Solvatochromism, Aggregation and Photochemical Properties of Fullerenes, $C_{60} and C_{70}$, in Solution

  • Nath, Sukhendu;Pal, Haridas;Sapre, Avinash.V.;Mittal, Jai.P.
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.105-119
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    • 2003
  • Fullerenes, $C_{60}$ and $C_{70}$, display interesting physicochemical properties in solutions, especially due to their unique chemical structures and their good electron accepting abilities. Solubility of fullerenes in different organic solvents and their unusual solvatochromic behavior, the ability of the fullerenes to form aggregates in solutions, and their electron transfer and charge transfer interactions with variety of electron donors, are the subjects of extensive research activities for more than one decade. Many research groups including ours have contributed substantially in the understanding of the solvatochromism, aggregation behavior, and the photoinduced electron transfer and charge transfer chemistry of fullerenes, in condensed phase. Present article is aimed to summarize the important results reported on the above aspects of fullerenes, subsequent to the earlier report from our group (D.K. Palit and J.P. Mittal, Full. Sci. & Tech. 3, 1995, 643-659).)., 643-659)..

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Nonlinear absorption in charge transfer films

  • Cha, M.;Sariciftici, N.S.;Heeger, A.J.;Hummelen, J.C.;WudI, F.
    • Proceedings of the Optical Society of Korea Conference
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    • 1995.06a
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    • pp.161-168
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    • 1995
  • Nonlinear optical absorption in solid films of poly(3-octyl thiophene) (P3OT) sensitized with methanofullerene was inverstigated for wacelengths from 620 to 960nm. The nonlinear absorption is ehnanced over that in either of the component materials by more than two orders orders of magitude at 760nm. The large nonlinearity results from effient photoinduced interm olecular charge transfer from P3OT to methanofullerene, followed by absorption in the charge separated excited state. P3OT/fullerene films are promising as reverse saturable absorbers and the optical limiting performance is demonstrated at 760nm.

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Photoinduced Hydrophilicity of Heterogeneous TiO2/WO3 Double Layer Films (이종 접합 구조를 갖는 TiO2/WO3 이중 박막의 광유기 친수 특성)

  • Oh, Ji-Yong;Lee, Byung-Roh;Kim, Hwa-Min;Lee, Chang-Hyun
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.28 no.11
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    • pp.715-720
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    • 2015
  • The photoinduced hydrophilicity of $TiO_2/WO_3$ double layer films was fabricated by using a conventional rf-magnetron sputtering method. The photoinduced hydrophilic reaction of the $TiO_2$ surface was enhanced by the presence of $WO_3$ under the $TiO_2$ layer by irradiation of a 10 W cylindrical fluorescent light bulb. However, when the $TiO_2$ and $WO_3$ layers were separated by an insulating layer, the surface did not appeared high hydrophilic, under the same light bulb. The enhanced photoinduced hydrophilic reaction can be explained by the charge transfer between $TiO_2$ and $WO_3$ layers. It was also demonstrated that visible light passing through the $TiO_2$ layer could excite $WO_3$. Thus, visible light can be used for the hydrophilic reaction in the present $TiO_2/WO_3$ system.

Thermodynamic Control in Competitive Anchoring of N719 Sensitizer on Nanocrystalline $TiO_2$ for Improving Photoinduced Electrons

  • Lim, Jong-Chul;Kwon, Young-Soo;Song, In-Young;Park, Sung-Hae;Park, Tai-Ho
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.68-69
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    • 2011
  • The process of charge transfer at the interface between two semiconductors or between a metal and a semiconductor plays an important role in many areas of technology. The optimization of such devices requires a good theoretical description of the interfaces involved. This, in turn, has motivated detailed mechanistic studies of interfacial charge-transfer reactions at metal/organic, organic/organic, and organic/inorganic semiconductor heterojunctions. Charge recombination of photo-induced electron with redox species such as oxidized dyes or triiodide or cationic HTM (hole transporting materials) at the heterogeneous interface of $TiO_2$ is one of main loss factors in liquid junction DSSCs or solid-state DSSCs, respectively. Among the attempts to prevent recombination reactions such as insulating thin layer and lithium ions-doped hole transport materials and introduction of co-adsorbents, although co-adsorbents retard the recombination reactions as hydrophobic energy barriers, little attention has been focused on the anchoring processes. Molecular engineering of heterogeneous interfaces by employing several co-adsorbents with different properties altered the surface properties of $TiO_2$ electrodes, resulting to the improved power conversion efficiency and long-term stability of the DSSCs. In this talk, advantages of the coadsorbent-assisted sensitization of N719 in preparation of DSSCs will be discussed.

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Fluorescent Compounds Having the Spaced and Integrated Type Receptors

  • Choi, Chang-Shik
    • Rapid Communication in Photoscience
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    • v.5 no.1
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    • pp.1-7
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    • 2016
  • Fluorescent receptors have gained much attention because of their usefulness in analysis and clarification of the roles of biomolecules in living systems. Molecular structures of the integrated type including that the receptor itself is fluorescent, and play an important role in having the functionality or selectivity of the fluorescent compounds. These spaced type fluorescent receptors are required to have special molecular design in order to transmit the information of molecular recognition to the fluorescent unit through the spacer unit. Compared with the spaced type fluorescent receptors, number of the integrated type receptors is limited due to the difficult molecular design and synthesis. Modification of alteration of the fluorophore frequently caused deterioration of the fluorescent property. Various spaced type and integrated type fluorescent receptors including switch on-off receptors are introduced in this article.

A Study on Photoreceptor by Using the Effect of Additives

  • Yu, Jin;Kim, Yeong Sun;Yu, Guk Hyeon
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.709-715
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    • 2001
  • We have been studied photosensitization mechanism's additive effect, of perylene 3,4,9,10-tetracarboxyl-diimide and X-phthalocyanine (charge generation materials), using the photochemical and photoelectrochemical approach. It was found that the photoreceptor on the excited state reacts with metal oxide, which creates the charge transfer on the interface of SnO2/electrolyte. In the electrode (X5P1) made of five X-phthalocyanine and single perylene 3,4,9,10-tetracarboxyldiimide layers, the cathodic photocurrent of X-phthalocyanine in the 400-600 nm region was increased by the addition of perylene 3,4,9,10-tetracarboxyldiimide. The maximum wavelength of fluorescence of perylene 3,4,9,10-tetracarboxyldiimide showed no dependence on the temperature. The addition of 4-dibenzylamino-2-methylbenzaldehyde diphenylhydrazone known as charge transport material was represented as decreasing photocurrent for X-phthalocyanine and perylene 3,4,9,10-tetracarboxyldiimide, respectively. In the electrode (X1P1) made of single X-phthalocyanine and single perylene 3,4,9,10-tetracarboxyldiimide layers, an anodic photocurrent of about 10.5 nA was generated by addition of hydroquinone at 550 nm. And the characteristic of photoinduced discharge was shown to decrease by a factor of 5 and the speed of dark decay was increased by a factor of 1.2.