Luminescent Triphosphine Cyanide d10 Metal Complexes

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• 作者：Gomathy Chakkaradhari ; Yi-Ting Chen ; Antti J. Karttunen ; Minh Thuy Dau ; Janne Jänis ; Sergey P. Tunik ; Pi-Tai Chou ; Mei-Lin Ho ; Igor O. Koshevoy
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：March 7, 2016
• 年：2016
• 卷：55
• 期：5
• 页码：2174-2184
• 全文大小：621K
• ISSN：1520-510X

文摘

Coinage metal cyanides efficiently react with a triphosphine. PPh₂C₆H₄–PPh–C₆H₄PPh₂ (P³). to give the complexes M(P³)CN, where M = Cu (1), Ag (2), and Au (3), which can further interact with coordinatively unsaturated metal centers [M(P³)]⁺ to give the homobimetallic [(P³)M–CN–M(P³)]⁺X^– [M = Cu (4a with X^– = CF₃SO₃^– and 4b with X^– = BF₄^–), Ag (5)] or heterometallic [(P³)Au–CN–Ag(P³)]⁺ (6) species. Extension of this approach also provided the trinuclear complex [(P³)Cu–NC–Au–CN–Cu(P³)]⁺ (7). Compounds 1–5 were characterized in the solid state by X-ray crystallography. The NMR spectroscopic studies revealed that all of the complexes except 6 retain their structures in solution. The title compounds are luminescent in the solid state, with quantum yields ranging from 8 to 87%. The observed photoemission originates mainly from the metal-to-ligand charge-transfer states according to time-dependent density functional theory computational studies. The crystalline bimetallic Cu complexes 4a/4b demonstrate extremely high sensitivity of the emission intensity to molecular O₂ (K_SV1 = 639 atm^–1 and LOD = 0.010% for 3 times the signal-to-noise ratio).