Influence of bridge topology and torsion on the intramolecular electron transfer.
To study molecules able to act as good "molecular wires", intramolecular electron transfer between two triphenylmethyl redox centers connected by bridges with different topologies and substituents have been studied in solution, both by UV-Vis-NIR and EPR spectroscopies. The synthetic methodology used allows a complete control of the geometry of polychlorotriphenylmethyl diradicals 1 and 2, which have para and meta topologies, respectively, as well as of their E/Z isomerism. This fact is used to show the influence of the different topologies in the ease of electron transfer, which is larger for the para than for the meta isomer where a small or negligible electronic coupling is observed. The related diradical 3 that have the same topology as the para isomer 1 but bearing two substituents on the central phenyl ring shows similar ease of electron transfer, that the para isomer 1.
Lloveras
Vega
V
Institut de Ciència de Materials de Barcelona (CSIC), Campus Universitari de Bellaterra, 08193 Cerdanyola, Spain.
Vidal-Gancedo
José
J
Ruiz-Molina
Daniel
D
Figueira-Duarte
Teresa M
TM
Nierengarten
Jean-François
JF
Veciana
Jaume
J
Rovira
Concepció
C