Cyclometalated Platinum(II) Cyanometallates: Luminescent Blocks for Coordination Self-Assembly

Research output: Contribution to journalArticleScientificpeer-review

Researchers

Research units

  • University of Würzburg
  • University of Eastern Finland
  • National Taiwan University

Abstract

A family of cyanide-bridged heterometallic aggregates has been constructed of the chromophoric cycloplatinated metalloligands and coordinatively unsaturated d10 fragments {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 (em = 16-34% em = 470-511 nm). The luminescence studies and time-dependent density functional theory computational analysis indicate that the photophysical behavior is dominated by the 3π-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.

Details

Original languageEnglish
Pages (from-to)4459-4467
Number of pages9
JournalInorganic Chemistry
Volume56
Issue number8
Publication statusPublished - 17 Apr 2017
MoE publication typeA1 Journal article-refereed

ID: 13437948