These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.


Pubmed for Handhelds

PUBMED FOR HANDHELDS

Search MEDLINE/PubMed

  • Title: Quantum chemical study of redox-switchable second-order nonlinear optical responses of D-π-A system BNbpy and metal Pt(II) chelate complex.
    Author: Ma NN, Sun SL, Liu CG, Sun XX, Qiu YQ.
    Journal: J Phys Chem A; 2011 Nov 24; 115(46):13564-72. PubMed ID: 21966928.
    Abstract:
    A second-order nonlinear optical (NLO) molecular switching with redox has been investigated in the present paper. The static first hyperpolarizabilities of 5-(BMes(2))-5'-(NPh(2))-2,2'-bipyridine (BNbpy) containing three-coordinate organoboron, Pt(II) chelate complex Pt(BNbpy)Ph(2), and their reduced forms have been calculated by density functional theory (DFT) combined with the analytic derivatives method. There is an enhancement of static first hyperpolarizabilities in the reduced form according to the calculations. That is, the β(vec) value of one-electron-reduced form is ~7 times as large as that of neutral form BNbpy; the β(vec) values of one- and two-electron-reduced forms are ~3 and ~4 times as large as that of neutral form Pt(BNbpy)Ph(2), respectively. In particular, the β(vec) value of two-electron-reduced form (3)Pt(BNbpy)Ph(2)(2-) is 1349 × 10(-30) esu, ~286 times larger than its neutral form. Moreover, the component β(z) value of the metal chelate complex Pt(BNbpy)Ph(2) is 25 × 10(-30) esu, which is ~14 times as large as that of ligand BNbpy; the corresponding F(-)/CN(-) compounds show a decrease in β(x) values compared with the case of the ligand and Pt(II) complex. Analyses of geometries, density of states (DOS), and time-dependent DFT (TDDFT) calculations reveal that the one-electron reduction promotes the molecular conjugation in the x-axis and intensifies the interaction between the metal Pt(II) and ligand and then results in an enhancement of the static first hyperpolarizability, whereas the binding of F(-)/CN(-) to the B atom turns off the p(π)-π* conjugation and has no effect on the conjugation of bipyridine, which leads to a decreasing β value in the x-axis.
    [Abstract] [Full Text] [Related] [New Search]