Premium
Phosphole‐Containing π‐Conjugated Systems: From Model Molecules to Polymer Films on Electrodes
Author(s) -
Hay Caroline,
Hissler Muriel,
Fischmeister Cédric,
RaultBerthelot Joëlle,
Toupet Loïc,
Nyulászi László,
Réau Régis
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20011001)7:19<4222::aid-chem4222>3.0.co;2-3
Subject(s) - phosphole , moiety , conjugated system , monomer , homo/lumo , polymer , molecule , electrochemistry , chemistry , absorption (acoustics) , photochemistry , materials science , electrode , organic chemistry , composite material
Two series of 2,5‐dipyridyl‐ and 2,5‐dithienylphosphole derivatives containing σ 3 ‐ or σ 4 ‐P atoms were prepared, and their optical (UV/Vis absorption, fluorescence spectra) and electrochemical properties were systematically evaluated. These physical properties depend mainly on the natures of the 2,5‐substituents and of the phosphorus moiety, and they revealed that these compounds contain extended π‐conjugated systems. Structure–property relationships were established on the basis of these experimental data and ab initio calculations on the parent molecules. The limited aromatic character and low‐lying LUMO of the phosphole ring appear to be crucial for achieving a highly delocalised π system. Electrooxidation of 2,5‐dithienylphosphole derivatives affords electroactive films with low optical band gaps. As observed for the corresponding monomers, the optical and electrochemical properties of the polymers can be varied over a wide range by modifying the nature of the phosphorus moiety.