Optoelectronic and nonlinear optical properties of triarylamine helicenes: a DFT study.

This work involved the design of a new series of triarylaminehelicenes (TAH) with significant hole transport capacity and enhanced nonlinear optical response. The geometries, electronic properties and nonlinear response of TAH derivatives were studied using density functional theory at the B3PW91/6-311++G (2d, 2p) level. Charge transfer and nonlinear optical response were analyzed and correlated with modifications in geometry and energy levels. Calculations indicated that trivial changes in the torsional angle occur in TAH derivatives with electron-donating substituents as compared to those with electron-withdrawing substituents, resulting in lower reorganization energies for TAH derivatives 2-6. TAH derivatives with an -N(CH3)2 group have the greatest highest occupied molecular orbital (HOMO) level, and thus the least ionization potential, indicating significant hole transfer efficiency as compared to unsubstituted TAH. A decrease in the HOMO-LUMO gap occurs upon substitution with electron-releasing groups, whereas there is an increase in the case of -NO2, -COOH, and -CN TAH derivatives. Topological analysis of the HOMOs of the neutral molecules revealed that these orbitals are concentrated mainly in the helicene backbone, with an important contribution from fused phenyl rings, nitrogen atoms and carbonyl groups. However, the lowest unoccupied molecular orbitals (LUMO) are invariably constituted by fused phenyl rings without any contribution from the central nitrogen atom. Studying the effect of substitution on the nonlinear optical response of TAH derivatives, the calculated polarizability and hyperpolarizability at B3PW91/6-311++G (2d,2p) level of theory exhibited a prominent improvement as compared to unsubstituted TAH. Both electron-donating groups and electron-withdrawing groups result in a red shift in the electronic absorption bands of the substitution derivatives, in particular those with -N(CH3)2 and -NH2 groups.