کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1324063 | 1499941 | 2010 | 7 صفحه PDF | دانلود رایگان |

Density functional theory (DFT) combined with the finite field (FF) method has been carried out to investigate the switching nonlinear optical (NLO) action of the TEMPO-bound dithiolate ligands and metal (Pt, Pd) complexes. The TEMPO unit is a redox-active radical and can stably exist in different redox states (TEMPOH, TEMPO+, TEMPO, TEMPO−). The DFT–FF calculations show that a substantial enhancement in second-order polarizability has been obtained in TEMPO+-bound dithiolate ligand, with a value of 461 × 10−30 esu. It is because that the TEMPO moiety as donor strength has been lowered by one-electron-reduced, and then the TEMPO moiety becomes the acceptor character in one-electron-oxidized species 1L+. On the whole, the βtot values of metal complexes within their four different states exhibit excellent NLO switching characters. Thus, this kind of metal complexes has a possibility to be excellent switching second-order NLO materials. Among four states of the metal complexes, the radical PtL and hydroxylamine PtLH species are nonlinearity “on”, while the one-electron-oxidized 3PtL+ and one-electron-reduced 3PtL− species are nonlinearity “off”. It can be seen from the following the real process. Specifically, the electron-acceptor ability of the diimine ligand decreases within its reduction process. However, the electronic character of dithiolate ligand will be changed from electron-donor to electron-acceptor when it is oxidated.
The second-order polarizabilities of metal complexes within their four different states exhibit excellent NLO switching characters. Thus, this kind of metal complexes has a possibility to be excellent switching second-order NLO materials. Among four states of the metal complexes, the radical PtL and hydroxylamine PtLH species are nonlinearity “on”, while the one-electron-oxidized 3PtL+ and one-electron-reduced 3PtL− species are nonlinearity “off”.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 695, Issues 19–20, 1–15 September 2010, Pages 2251–2257