Spectroscopic and theoretical study of the molecular and electronic structures of a terthiophene-based quinodimethane

被引:45
作者
Casado, J [1 ]
Pappenfus, TM
Mann, KR
Ortí, E
Viruela, PM
Milián, B
Hernández, V
Navarrete, JTL
机构
[1] Univ Valencia, Inst Ciencia Mol, E-46100 Valencia, Spain
[2] Univ Malaga, Dept Quim Fis, E-29071 Malaga, Spain
[3] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
关键词
density functional calculation; electronic spectroscopy; oligothiophenes; thin films; vibrational spectroscopy;
D O I
10.1002/cphc.200300963
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The UV/Vis, infrared absorption, and Raman scattering spectra of 3',4'-dibutyl-5,5"-bis(dicyanomethylene)-5,5"-dihydro-2,2':5',2"-terthiophene have been analyzed with the aid of density functional theory calculations. The compound exhibits a quinoid structure in its ground electronics state and presents an intramolecular charge transfer from the terthiophene moiety to the C(CN)(2) groups. The molecular system therefore consists of an electron-deficient terthiophene backbone end-capped with electron rich C(CN)(2) groups. The molecule is characterized by a strong absorption in the red, due to the HOMO-->LUMO pi-pi* electronic transition of the terthiophene backbone that shifts hypsochromically on passing from the solid state to solution and with the polarity of the solvent. The analysis of the vibrational spectra confirms the structural conclusions and supports the existence of an intramolecular charge transfer. Vibrational spectra in several solvents and as a function of temperature has also been studied. Significant frequency upshifts of the vibrations involved in the pi-electron conjugated pathway have been noticed upon solution in polar solvents and with the lowering of the temperature. Finally, we purpose a quinoid molecule as a reliable structural and electronic model for dication species in doped oligothiophenes or for bipolaron charged defects in doped polythiophene.
引用
收藏
页码:529 / 539
页数:11
相关论文
共 93 条
  • [1] Electronic and dynamical effects from the unusual features of the Raman spectra of oligo and polythiophenes
    Agosti, E
    Rivola, M
    Hernandez, V
    Del Zoppo, M
    Zerbi, G
    [J]. SYNTHETIC METALS, 1999, 100 (01) : 101 - 112
  • [2] Characterization of the quinoid structure for the 2,2'-bithiophene and 2,2',5',2''-terthiophene dications
    Aleman, C
    Julia, L
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (35) : 14661 - 14664
  • [3] A study of sulphur-containing molecules using Hartree-Fock, MP2 and DFT (hybrid) methodologies
    Altmann, JA
    Handy, NC
    Ingamells, VE
    [J]. MOLECULAR PHYSICS, 1997, 92 (03) : 339 - 352
  • [4] Recent advances in the description of solvent effects with the polarizable continuum model
    Amovilli, C
    Barone, V
    Cammi, R
    Cancès, E
    Cossi, M
    Mennucci, B
    Pomelli, CS
    Tomasi, J
    [J]. ADVANCES IN QUANTUM CHEMISTRY, VOL 32: QUANTUM SYSTEMS IN CHEMISTRY AND PHYSICS, PT II, 1998, 32 : 227 - 261
  • [5] BAUERLE P, 1993, J AM CHEM SOC, V115, P10217
  • [6] BAUERLE P, 1993, ANGEW CHEM INT EDIT, V32, P76, DOI 10.1002/anie.199300761
  • [7] Experiment versus time dependent density functional theory prediction of fullerene electronic absorption
    Bauernschmitt, R
    Ahlrichs, R
    Hennrich, FH
    Kappes, MM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (20) : 5052 - 5059
  • [8] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
    BECKE, AD
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) : 5648 - 5652
  • [9] Excited-state electronic structure of conjugated oligomers and polymers:: A quantum-chemical approach to optical phenomena
    Brédas, JL
    Cornil, J
    Beljonne, D
    dos Santos, D
    Shuai, ZG
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 1999, 32 (03) : 267 - 276
  • [10] Quinonoid oligothiophenes as electron-donor and electron-acceptor materials.: A spectroelectrochemical and theoretical study
    Casado, J
    Miller, LL
    Mann, KR
    Pappenfus, TM
    Higuchi, H
    Ortí, E
    Milián, B
    Pou-Amérigo, R
    Hernández, V
    Navarrete, JTL
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (41) : 12380 - 12388