Structural modelling of optical and electrochemical properties of 4-aminodiphenylamines - optoelectronic studies on a polyaniline repeating unit.
Amino-diphenylanilines and their planarized and twisted model compounds have been investigated by steady state and time-resolved absorption and emission, as well as by spectroelectrochemistry. These polyaniline model compounds show that the observation of excited states with full charge separation is linked to molecular twisting where the diaminobenzene is the donor and the phenyl group the acceptor. The observable charge transfer fluorescence shows the characteristic features of twisted intramolecular charge transfer (TICT) excited states, i.e. forbidden emissive properties and strong solvatochromic red shift. The transient absorption spectrum of the TICT state matches the ground state absorption spectrum of the electrochemically produced radical cation of the molecule. This is the first example where excited-state properties of the neutral and ground state properties of the radical cation are directly linked.
Malval
Jean Pierre
JP
Laboratoire d'Analyse Chimique par Reconnaissance Moléculaire, Ecole Nationale Supérieure de Chimie et de Physique de Bordeaux, Pessac, France.
Morand
Jean Pierre
JP
Lapouyade
René
R
Rettig
Wolfgang
W
Jonusauskas
Gediminas
G
Oberlé
Jean
J
Trieflinger
Christian
C
Daub
Joerg
J
D000814:Aniline Compounds / Q000737:chemistry*; D004563:Electrochemistry / Q000379:methods; D004581:Electronics; D006863:Hydrogen-Ion Concentration; D008956:Models, Chemical; D015394:Molecular Structure; D055095:Optics and Photonics; D010084:Oxidation-Reduction; D010655:Phenylenediamines / Q000737:chemistry*; D013050:Spectrometry, Fluorescence / Q000379:methods; D013054:Spectrophotometry, Atomic / Q000379:methods; D013997:Time Factors
D000814:Aniline Compounds; D010655:Phenylenediamines; C416807:polyaniline; C031506:4-aminodiphenylamine