Quantification of the push-pull character of azo dyes and a basis for their evaluation as potential nonlinear optical materials

The push-pull characters of a large series of donor-acceptor substituted azo dyes-71 structures in all-have been quantified by the NN double bond lengths, dNN, the 15N NMR chemical shift differences, Δδ15N, of the two nitrogen atoms and the quotient, π∗/π, of the occupations of the antibonding π∗, and bonding π orbitals of this partial NN double bond. The excellent correlation of the occupation quotients with the bond lengths strongly infers that both π∗/π and dNN are excellent parameters for quantifying charge alternation in the push-pull chromophore and the molecular hyperpolarizability, β0, of these compounds. By this approach, selected compounds can be appropriately considered as viable candidates for nonlinear optical (NLO) applications.