Luminescent Triphosphine Cyanide d(10) Metal Complexes

Inorganic Chemistry
Gomathy ChakkaradhariIgor O Koshevoy

Abstract

Coinage metal cyanides efficiently react with a triphosphine. PPh2C6H4-PPh-C6H4PPh2 (P(3)). to give the complexes M(P(3))CN, where M = Cu (1), Ag (2), and Au (3), which can further interact with coordinatively unsaturated metal centers [M(P(3))](+) to give the homobimetallic [(P(3))M-CN-M(P(3))](+)X(-) [M = Cu (4a with X(-) = CF3SO3(-) and 4b with X(-) = BF4(-)), Ag (5)] or heterometallic [(P(3))Au-CN-Ag(P(3))](+) (6) species. Extension of this approach also provided the trinuclear complex [(P(3))Cu-NC-Au-CN-Cu(P(3))](+) (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 (KSV1 = 639 atm(-1) and LOD = 0.010% for 3 times the signal-to-noise ratio).

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Citations

Mar 31, 2017·Inorganic Chemistry·Leon SchneiderIgor O Koshevoy
Aug 18, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Thuy Minh DauIgor O Koshevoy
Oct 7, 2016·Chemical Communications : Chem Comm·M El Sayed MoussaC Lescop
Aug 23, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Masahisa OsawaMikio Hoshino
Nov 28, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Wei-Jie GongJian-Ping Lang
Jun 14, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Zheng-Bang PanMei-Lin Ho
May 15, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Masahisa OsawaMunetaka Akita

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