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Electron‐Rich Tetrathiafulvalene–Triarylamine Conjugates: Synthesis and Redox Properties
Author(s) -
Li Hongchao,
Lambert Christoph
Publication year - 2006
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/chem.200500928
Subject(s) - moiety , tetrathiafulvalene , conjugate , pyrrole , materials science , electrochemistry , cyclic voltammetry , crystallography , chemistry , photochemistry , stereochemistry , molecule , organic chemistry , mathematical analysis , mathematics , electrode
By combining tetrathiafulvalenes (TTFs) and triarylamines, four TTF–triarylamine conjugates bridged by an annulated pyrrole ring were designed and synthesized by an N ‐arylation reaction. Electrochemical and photophysical investigations suggest that these novel conjugates possess very strong electron‐donating ability with very high HOMO energy levels of around −4.70 eV; the HOMOs are mainly located on the TTF moiety. We observed significant electronic coupling between the TTF moieties and the triarylamine groups. However, no evidence for such electronic communication between end‐capping TTF units (conjugates 5 and 7 ) or between two terminal triarylamine groups (conjugate 9 ) could be found. Differential scanning calorimetry (DSC) measurements together with PM3‐optimized geometries suggest that conjugates 5 and 7 , which adopt three‐dimensional propeller‐shaped structures, may easily pack and crystallize in the solid state because of the large rigid planar blades consisting of TTF and one of the phenyl rings of the triarylamine moiety. However, conjugate 9 , with two bulky end‐capping triarylamine groups, forms an amorphous material with a glass transition at 74.5 °C.