• Title/Summary/Keyword: intramolecular charge transfer

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Organic nonlinear optic materials for intergated optics and optical teclecommunications (집적광학과 광통신을 위한 비선형광학 유기물질)

  • 윤촌섭
    • Proceedings of the Optical Society of Korea Conference
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    • 1991.07a
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    • pp.5-8
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    • 1991
  • New nonliner organic materials have been developed for all-optical signal processing. The organic materials possess many interesting features for this purpose. Unlike inorganic molecules the delocalized $\pi$-electron distribution and intramolecular charge transfer mevhanism allows certain organic molecules to respond highly anharmonically to an external field. In the present paper the origins of nonlinear phenomena, advantages of orgnic materials and structures of organic devices will be discussed.

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SOLVATOCHROMIC BEHAVIOUR OF DONOR-ACCEPTOR SUBSTITUTED 1,2-DIPHENYLETHENES IN ORGANIC SOLVENTS, REVERSE MICELLES AND POLYMER MATRIX

  • Singh, A.K.;Mahalaxmi, G.R.;Malimath, G.H.
    • Journal of Photoscience
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    • v.4 no.2
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    • pp.53-59
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    • 1997
  • Absorption and fluorescence studies of E-1-(p-methoxyphenyl)-2-(p-nitrophenyl) ethene in homogeneous solvents, polymer matrix and normal and reverse micelles showing strong solvatochromic fluorescent emission properties with quasi-planar intramolecular charge transfer characteristics in the electronically excited singlet state are discussed.

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Temperature-Dependent Redox Isomerism via Intramolecular Electron Transfer. Synthesis and Properties of Co(dmppz)₂(3,6-dbq)₂ (dmppz=1,4-dimethylpiperazine; 3,6-dbq=3,6-di-tert-butyl-1,2-quinone)

  • 정옥상;조두환;박성호;손윤수
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.628-631
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    • 1997
  • The preparation and characterization of $Co(dmppz)_2(3,6-dbq)_2$ (dmppz=1,4-dimethylpiperazine; 3,6-dbq=3,6-di-tert-butyl-1,2-quinone) are established. Temperature-dependent magnetic moments (100-400 K), variable-temperature IR, and electronic spectra are presented to show that the title complex exhibits an equilibrium via a catechol to cobalt intramolecular electron transfer. At temperatures below 350 K, the charge distribution of the complex is $Co^Ⅲ(dmppz)_2(3,6-dbsq)(3,6-dbcat)$ (3,6-dbsq=3,6-di-tert-butyl-1,2-semiquinonato; 3,6-dbcat=3,6-di-tert-butylcatecholato) whereas at the temperature beyond 390 K, the complex is predominantly Co^Ⅱ(dmppz)_2(3,6-dbsq)_2$ form in the solid state. At the temperature range of 350-390 K a mixture of Co(Ⅲ) and Co(Ⅱ) redox isomers exist at equilibrium. The transition temperature (Tc) of Co(Ⅲ)/Co(Ⅱ) in solution is approximately 50° lower than that in the solid state. In particular, thermal analysis on solid sample of the complex discloses that the transition for the Co(Ⅲ)/Co(Ⅱ) is accompanied by the change in heat content of 12.30 kcal/mol.

Quenching of Ofloxacin and Flumequine Fluorescence by Divalent Transition Metal Cations

  • Park, Hyoung-Ryun;Oh, Chu-Ha;Lee, Hyeong-Chul;Choi, Jae-Gyu;Jung, Beung-In;Bark, Ki-Min
    • Bulletin of the Korean Chemical Society
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    • v.27 no.12
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    • pp.2002-2010
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    • 2006
  • This study examined the quenching of ofloxacin (OFL) and flumequine (FLU) fluorescence by $Cuj^{2+}$, $Ni^{2+}$, $Co^{2+}$ and $Mn^{2+}$ in an aqueous solution. The change in the fluorescence intensity and lifetime was measured at various temperatures as a function of the quencher concentration. According to the Stern-Volmer plots, the fluorescence emission was quenched by both collisions (dynamic quenching) and complex formation (static quenching) with the same quencher but the effect of static quenching was larger than that of dynamic quenching. Large static and dynamic quenching constants for both OFL and FLU support significant ion-dipole and orbital-orbital interactions between fluorophore and quencher. For both molecules, the static and dynamic quenching constants by $Cu^{2+}$ were the largest among all the metal quenchers examined in this study. In addition, both the static and dynamic quenching mechanisms by $Cu^{2+}$ were somewhat different from the quenching caused by other metals. Between $Ni^{2+}$ and FLU, a different form of chemical interaction was observed compared with the interaction by other metals. The change in the absorption spectra as a result of the addition of a quencher provided information on static quenching. With all these metals, the static quenching constant of FLU was larger than those of OFL. The fluorescence of OFL was quite insensitive to both the dynamic and static quenching compared with FLU. This property of OFL can be explained by the twisted intramolecular charge transfer in the excited state.

EXCITED-STATE TWISTED INTRAMOLECLILAR CHARGE TRANSFER OF p-N,N-DIMETHYLAMINOBENZOIC ACID IN AQUEOUS CYCLODEXTRIN SOLUTIONS: TIME-RESOLVED FLUORESCENCE STUDY

  • Kim, Yong-Hee;Cho, Dae-Won;Yoon, Min-Joong
    • Journal of Photoscience
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    • v.3 no.3
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    • pp.153-158
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    • 1996
  • The effects of $\alpha$- and $\beta$-cyclodextrins (CD) on the twisted intramolecular charge transfer (TICT) behavior of p-N,N'-dimethylaminobenzoic acid (DMABA) in buffered aqueous solution have been investigated by examining formation and decay behaviors of the TICT-typical dual fluorescence. The ratio of the TICT emission to the normal emission (I$_a$/I$_b$) increases linearly $\alpha$-CD concentration increases, while in the presence of $\beta$-CD it shows nonlinear dependences on the CD concentration. The analysis of the CD-dependent changes of the I$_a$/I$_b$ and absorption spectra demonstrates formation of 1:1 inclusion complexes between DMABA and CDs. The decay time of the normal emission (ca. 700 ps) is little affected by the formation of $\alpha$-CD inclusion complex, whereas it increases upto ca. 1.6 ns upon formation of $\beta$-CD inclusion complex. The TICT emission for the $\beta$-CD inclusion complex exhibits two decay components while it shows a single component for the $\alpha$-CD inclusion complex, indicating formation of one or two types of inclusion complex in the presence of $\alpha$-CD or $\beta$-CD, respectively. These results are attributed to the CD cavity size dependence on patterns of complexation between CDs and DMABA. The CD size dependences of the TICT fluorescence properties with the orientation of the guest molecule demonstrate that the specific hydrogen bonding between the carboxylic acid group and water plays an important role in the excited-state TICT.

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Fluorescence Behavior Associated with a Possible Intercolumnar Charge-transfer Interaction in the Crystalline State of a Dyad Consisting of Mesitylene and 1,4-Dicyano-2-methylnaphthalene Subunits

  • Ohta, Eisuke;Kobayashi, Hitoshi;Sakai, Atsushi;Matsui, Yasunori;Sato, Hiroyasu;Ikeda, Hiroshi
    • Rapid Communication in Photoscience
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    • v.4 no.2
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    • pp.31-33
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    • 2015
  • Fluorescence (FL) properties of a novel donor-acceptor dyad, comprised of mesitylene and 1,4-dicyano-2-methylnaphthalene (DCMN) subunits connected by an ether linkage, were elucidated. The dyad in cyclohexane exhibits FL arising from an intramolecular exciplex. In the crystalline state, the dyad does not emit light from intra- and inter-molecular exciplexes but rather displays FL that is nearly equivalent to that of 2-methoxymethyl-substituted DCMN. However, the emission spectrum of the crystalline dyad contains a shoulder in the long wavelength region, suggesting that weak intercolumnar charge-transfer interactions take place between columns consisting of the mesitylene and DCMN subunits.

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.

Optical Transmittance of Polybenzoxazole Precursor (폴리벤조옥사졸 전구체의 광투과도 연구)

  • 김대겸;김종화;최길영;오재민;이무영;박동원;이광섭;진문영
    • Polymer(Korea)
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    • v.26 no.1
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    • pp.18-27
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    • 2002
  • Poly(ο-hydroxyamide)s as polybenzoxazoles precursors were synthesized by polycondensation from 2,2'-bis(3-amino-4-hydroxyphenyl) hexafluoropropane and various bis-acids. And the polymers were modified to acid-sensitive polyamides by introducing tetrahydropyran in order to impart photosensitivity. A study of optical transmittance at 365 nm, according to the chemical structure of bis-acid, revealed that the polymer derived from 4,4'-oxydibenzoic acid showed better optical transparency than those from other bis-acids. This tendency of optical transmittance could be explained by formation of charge transfer complex. In case of the polymer derived from 4,4'-oxydibenzoic acid, the electron accepting characteristic of bis-acid is reduced by introduction of electron donating group, -O-. Thus, optical transmittance increased due to the diminished formation of intramolecular charge transfer complex. In addition, the optical transmittance increased with increasing the THP content in the polymer. This is attributed to the reduced intermolecular interaction by the loosening of the packing density of the polymer chain.

Synthesis, Characterizations, and Intramolecular Quenching Behavior of an Axially-Linked Trinuclear Molecular Wire Containing Ruthenium(II) Porphycenes

  • Abe, Masaaki;Ashigara, Shiho;Okawara, Toru;Hisaeda, Yoshio
    • Rapid Communication in Photoscience
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    • v.4 no.1
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    • pp.22-24
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    • 2015
  • A new trinuclear complex $[Ru(TPrPc)(CO)]_2[Ru(pytpy)_2](PF_6)_2$ (TPrPc = 2,7,12,17-tetra-n-propylporphycenato dianion and pytpy = 4'-(4-pyridyl)-2,2':6',2"-terpyridine) has been synthesized and characterized as the first example of a discrete molecular wire containing metalloporohycenes as a building block. The trinuclear complex shows multiple-step redox behavior in 0.1 M n-$Bu_4NPF_6$-dichloromethane. The mononuclear $[Ru(pytpy)_2]^{2+}$ precursor shows emission at 640 nm (deaerated acetone, 298 K) upon illumination at the metal-to-ligand charge transfer (MLCT) band at 495 nm, but the trinuclear molecular wire is found to be non-emissive upon photoexcitation at the central $[Ru(pytpy)_2]^{2+}$ entity, indicating an efficient quenching ability of the axially-linked, ruthenium(II)-porphycene chromophores in an intramolecular fashion.