Mechanistic insight into the second-order nonlinear optical properties of Ru-coordinated DTE complexes: Photoisomerization, redox, and protonation switches

作者：Tian, Dong-Mei; Ma, Na-Na; Wang, Wen-Yong; Wang, Jiao; Zhu, Chang-Li; Qiu, Yong-Qing^*

来源：Journal of Organometallic Chemistry, 2014, 772: 100-106.

DOI：10.1016/j.jorganchem.2014.08.010

• Ru complex
• NLO response
• Switching
• DFT

In this paper, the switchable second-order nonlinear optical (NLO) responses of Ru dithienylperfluorocyclopentene (DTE) complexes controlled by photoisomerization, oxidation and protonation have been systematically investigated by the density functional theory. Theoretical results reveal some important structural changes upon these three pathways. It can also be found that the protonation and oxidation processes have some infuence on the charge transfer (Cr) pattern but slightly affect the first hyperpolarizability (beta(vec)). In striking contrast, in the photoisomerization process, the difference on the Ovec values between 2o and 2c is the largest with respect to the protonation and oxidation processes with beta(vec)(2C)/beta(vec)(2o) = 52.7 ratio. Time-dependent density functional theory calculation predicts that the DTE intramolecular pi-pi* charge transfer is helpful for the large NLO response. It confirms that the photoirradiation evokes the photoisomerization character to display dramatic difference in beta(vec) values, which paves the way for the applications of switchable NLO materials.

• 出版日期2014-12-1
• 单位东北师范大学