Theoretical study of the second-order nonlinear optical properties of [N]helicenes and [N]phenylenes

The second-order nonlinear optical properties of helicenes and phenylenes have been theoretically investigated at the time-dependent Hartree-Fock level using the Austin model 1 semiempirical Hamiltonian. Both the antisymmetric isotropic component of the first hyperpolarizability (beta) and its projection on the dipole moment (beta(parallel)) have been determined for increasingly large helical systems as well as for their analogs substituted by donor/acceptor pairs. It is found that (i) in nonsubstituted helicenes and phenylenes, beta increases monotonically with the size of the system and slightly depends on the nature of the helix; (ii) the corresponding beta(parallel) is mostly determined by the radial component of the first hyperpolarizability vector; (iii) in helicenes, beta(parallel) is positive and presents quasiperiodic oscillations with the helix; (iv) in phenylenes, beta(parallel) depends upon the size of the helix and it can be either positive or negative as a result of the differences in evolution with N of the radial components of the dipole moment and first hyperpolarizability. Substituting the helicenes and phenylenes by the prototypical NH2/NO2 donor/acceptor pair provides a diversity of effects on beta and beta(parallel) that encompasses decrease, increase, and change in sign.