Theoretical investigation on second-order nonlinear optical properties of ruthenium alkynyl-dihydroazulene/vinylheptafulvene complexes.

Ru metal acetylide electron donor-acceptor complexes have important applications in the field of nonlinear optics. Herein, in this work, a series of half-sandwich ruthenium-based Cp*(dpe)Ru ([Ru*]) metal complexes with the dihydroazulene/vinylheptafulvene (DHA/VHF) have been investigated by density functional theory (DFT) calculations. The results showed that the position of the [Ru*] acetylide functionality, either para or meta on the phenylene ring to the DHA/VHF core (1c/1o and 2c/2o), and additional a p-phenylene spacer (3c/3o) had a great influence on the second-order nonlinear optical (NLO) responses. The systems 1 and 3 can significantly increased second-order NLO responses compared with system 2. It was attributed to the more obvious charge transfer along y-axis, which is from [Ru*] acetylide functionality to DHA, accompanied by a significant decrease of the transition energy according electron density difference maps and time-dependent DFT calculations. The β values of the open-ring complexes were larger than the corresponding closed-ring complexes owing to the smaller HOMO-LUMO gap in the open-ring complexes. It was also because of the smaller BLA values in open-ring complexes, which had stronger π-conjugation. Especially, the change ratio of β value of system 2 was the largest due to the fact that their charge transfers degree varied greatly. In addition, the frequency-dependent NLO properties of the studied complexes were evaluated at 0.0239 a.u. and 0.0340 a.u. The calculation results demonstrated that the magnitude of the frequency-dependent first hyperpolarizability increased with the increasing frequency. We believe that our present work will be beneficial for further theoretical and experimental studies on large second-order NLO responses of metal complexes.