Uniting Ruthenium(II) and Platinum(II) Polypyridine Centers in Heteropolymetallic Complexes Giving Strong Two-Photon Absorption

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• 作者：Pengfei Shi ; Benjamin J. Coe ; Sergio S谩nchez ; Daqi Wang ; Yupeng Tian ; Marcin Nyk ; Marek Samoc
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 7, 2015
• 年：2015
• 卷：54
• 期：23
• 页码：11450-11456
• 全文大小：425K
• ISSN：1520-510X

文摘

New trinuclear RuPt₂ and heptanuclear RuPt₆ complex salts are prepared by attaching Pt^II 2,2鈥?6鈥?2鈥?terpyridine (tpy) moieties to Ru^II 4,4鈥?2鈥?2鈥?4鈥?4鈥?quaterpyridine (qpy) complexes. Characterization includes single crystal X-ray structures for both polymetallic species. The visible absorption bands are primarily due to Ru^II 鈫?qpy metal-to-ligand charge-transfer (MLCT) transitions, according to time-dependent density functional theory (TD-DFT) calculations. These spectra change only slightly on Pt coordination, while the orange-red emission from the complexes shows corresponding small red-shifts, accompanied by decreases in intensity. Cubic molecular nonlinear optical behavior has been assessed by using Z-scan measurements. These reveal relatively high two-photon absorption (2PA) cross sections 蟽₂, with maximal values of 301 GM at 834 nm (RuPt₂) and 523 GM at 850 nm (RuPt₆) when dissolved in methanol or acetone, respectively. Attaching Pt^II(tpy) moieties triples or quadruples the 2PA activities when compared with the Ru^II-based cores.