title: Cyclometalated Platinum(II) Cyanometallates: Luminescent Blocks for Coordination Self-Assembly.
abstract: A family of cyanide-bridged heterometallic aggregates has been constructed of the chromophoric cycloplatinated metalloligands and coordinatively unsaturated d10fragments {M(PPh3)n}. The tetranuclear complexes of general composition [Pt(C^N)(CN)2M(PPh3)2]2[C^N = ppy, M = Cu (1), Ag (2); C^N = tolpy (Htolpy = 2-(4-tolyl)-pyridine), M = Cu (4), Ag (5); C^N = F2ppy (HF2ppy = 2-(4, 6-difluorophenyl)-pyridine), M = Cu (7), Ag (8)] demonstrate a squarelike arrangement of the molecular frameworks, which is achieved due to favorable coordination geometries of the bridging ligands and the metal ions. Variation of the amount of the ancillary phosphine (for M = Ag) afforded compounds [Pt(C^N)(CN)2Ag(PPh3)]2(C^N = ppy, 3; C^N = tolpy, 6); for the latter one an alternative cluster topology, stabilized by the Pt-Ag metallophilic and η1-Cipso(C^N)-Ag bonding, was observed. The solid-state structures of all of the title species 1-8 were determined crystallographically. The complexes exhibit moderately strong room-temperature phosphorescence as crystalline powders (Φem= 16-34%, λem= 470-511 nm). The luminescence studies and time-dependent density functional theory computational analysis indicate that the photophysical behavior is dominated by the3π-π* electronic transitions localized on the cyclometalated fragment and mixed with MPtLCT contribution, while the d10-phosphine motifs have a negligible contribution into the frontier orbitals and therefore show a little influence on the emission performance of the described compounds.
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität , Würzburg, Germany.|Department of Chemistry, University of Eastern Finland , 80101 Joensuu, Finland.
authors.forename: Leon
authors.initials: L
authors.lastname: Schneider
authors.affiliation: Department of Chemistry, University of Eastern Finland , 80101 Joensuu, Finland.
authors.forename: Vasily
authors.initials: V
authors.lastname: Sivchik
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 106, Taiwan.
authors.forename: Kun-You
authors.initials: KY
authors.lastname: Chung
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 106, Taiwan.
authors.forename: Yi-Ting
authors.initials: YT
authors.lastname: Chen
authors.affiliation: Department of Chemistry, Aalto University , FI-00076 Aalto, Finland.
authors.forename: Antti J
authors.identifier: http://orcid.org/0000-0003-4187-5447
authors.initials: AJ
authors.lastname: Karttunen
authors.affiliation: Department of Chemistry, National Taiwan University , Taipei 106, Taiwan.
authors.forename: Pi-Tai
authors.identifier: http://orcid.org/0000-0002-8925-7747
authors.initials: PT
authors.lastname: Chou
authors.affiliation: Department of Chemistry, University of Eastern Finland , 80101 Joensuu, Finland.
authors.forename: Igor O
authors.identifier: http://orcid.org/0000-0003-4380-1302
authors.initials: IO
authors.lastname: Koshevoy