| Popis: |
Owing to their odd order, second-order nonlinear optical (NLO) responses are very sensitive to symmetry. Therefore, within hyper-Rayleigh scattering (HRS) technique, the symmetry impacts the amplitude of the molecular responses, the HRS first hyperpolarizability (β HRS), and the depolarization ratio (DR). Starting from a challenging octupolar structure bearing six ruthenium(II) ammine centers π-conjugated via quaterpyridyl moieties to a tris-chelated zinc(II) core, together with its Λ shape and one-dimensional analogues built by replacing one or two Ru-quaterpyridyl moieties with bipyridine moieties, (time-dependent) density functional theory calculations have been enacted to unravel the symmetry–NLO response relationships as well as their Ru II/III redox-triggered switching effects. The one-dimensional and Λ-shaped NLOphores present β HRS values ∼3 times larger than those of the octupolar system, for both Ru oxidation states. However, using the few-state valence bond-charge transfer models demonstrates that the β HRS response of the octupolar complex cation can become larger than those of its one-dimensional and Λ-shaped analogues provided stronger donor–acceptor groups are employed. In parallel, the DRs decrease from a strong dipolar character (DR ≈ 6) for the one-dimensional chromophore to a weaker dipolar character (DR ≈ 5) for the Λ-shaped one and to a clear octupolar character (DR ≈ 1.7) for the last one. In all cases, the β responses originate mostly from metal-to-ligand charge transfer excited states, as revealed using a new scheme for analyzing the variations in electron density upon excitation. The Ru II/III oxidations lead to a strong decrease in the β HRS responses, which is attributed to the loss of the donor character of the Ru centers and therefore to the reduction of the push–pull π-conjugation. These results demonstrate that the NLO contrast and the NLO switching behavior of these Ru cations are maintained for the different molecular symmetries. Finally, the character of the β responses of the oxidized species, as revealed by the DR values, further evidences a clear evolution from dipolar to octupolar NLOphores. |
