C. Lambert et al., Subchromophore interactions in tricyanovinyl-substituted triarylamines - acombined experimental and computational study, J CHEM S P2, (3), 1999, pp. 577-587
Citations number
86
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
The electronic coupling between the phenyl substituents of mono-, bis-, and
tris(tricyanovinyl)-substituted triphenylamines (1, 2, 2-OMe and 3) have b
een investigated by various methods: the splitting of excited states was ta
ken as a measure of the interaction. These splittings can be seen in the op
tical absorption spectra; exciton coupling theory was also used to estimate
electronic coupling of the excited states; redox potentials gave coupling
energies of charged ground state species as well as Hush analysis of interv
alence charge-transfer bands (IV-CT), which were observed by UV-Vis-NIR spe
ctroelectrochemistry, and finally, the quadratic hyperpolarisability measur
ed by hyper-Rayleigh scattering was used to estimate excited state coupling
s. The results of these methods were compared to semiempirical AM1 calculat
ions and suggest the subchromophore interactions to be weak compared to the
band width of the UV-spectra. Nevertheless, the quadratic hyperpolarisabil
ity is enhanced in the two-dimensional tris(tricyanovinylphenyl)amine compa
red to its one-dimensional analogue.