title: Luminescent Triphosphine Cyanide d(10) Metal Complexes.
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).
authors.affiliation: University of Eastern Finland , Department of Chemistry, 80101, Joensuu, Finland.
authors.forename: Gomathy
authors.initials: G
authors.lastname: Chakkaradhari
authors.affiliation: National Taiwan University , Department of Chemistry, Taipei 106, Taiwan.
authors.forename: Yi-Ting
authors.initials: YT
authors.lastname: Chen
authors.affiliation: Aalto University , Department of Chemistry, 00076 Aalto, Finland.
authors.forename: Antti J
authors.initials: AJ
authors.lastname: Karttunen
authors.affiliation: University of Eastern Finland , Department of Chemistry, 80101, Joensuu, Finland.
authors.forename: Minh Thuy
authors.initials: MT
authors.lastname: Dau
authors.affiliation: University of Eastern Finland , Department of Chemistry, 80101, Joensuu, Finland.
authors.forename: Janne
authors.initials: J
authors.lastname: Jänis
authors.affiliation: St. Petersburg State University , Department of Chemistry, Universitetskii pr. 26, 198504, St Petersburg, Russia.
authors.forename: Sergey P
authors.initials: SP
authors.lastname: Tunik
authors.affiliation: National Taiwan University , Department of Chemistry, Taipei 106, Taiwan.
authors.forename: Pi-Tai
authors.initials: PT
authors.lastname: Chou
authors.affiliation: Soochow University , Department of Chemistry, Taipei, Taiwan.
authors.forename: Mei-Lin
authors.initials: ML
authors.lastname: Ho
authors.affiliation: University of Eastern Finland , Department of Chemistry, 80101, Joensuu, Finland.
authors.forename: Igor O
authors.initials: IO
authors.lastname: Koshevoy