Synthesis of pendant-type anthraquinone-bridged cofacial dinuclear platinum(II) complexes and their emission properties

Inorg Chem. 2007 Dec 24;46(26):11291-6. doi: 10.1021/ic700953k. Epub 2007 Nov 29.

Abstract

Anthraquinone-bridged mononuclear and dinuclear complexes, [PtCl(AQ-amide-tpy)](PF6) (1), [Pt2Cl2(AQ-amide-tpy2)](PF6)2 (2), and [Pt2Cl2(AQ-eth-tpy2)](PF6)2 (3), were synthesized and their photochemical properties were investigated. Amide-bound mononuclear complex 1 exhibited only metal-to-ligand charge transfer (MLCT) absorption and emission, whereas dinuclear complex 2 exhibited a low-energy emission around 700 nm at room temperature. Emission lifetime analysis indicated that this emission was originated from the metal-metal-to-ligand charge transfer (MMLCT) excited state, implying the existence of an intramolecular Pt-Pt interaction at the photoexcited state. 3 with rigid ethynylene linkers showed a low-energy absorption around 520 nm (epsilon = approximately 1100 M(-1) cm(-1)) in addition to an 1MLCT absorption, which was ascribed to a 3MLCT absorption from the consideration of the Pt-Pt distance on a geometry-optimized structure. The emission of 3 appeared at 600 nm, which is higher in energy compared with the emission of 2. It is postulated that the restriction of the Pt-Pt distance flexibility in the rigid structure of 3 prevents the significant increase of the Pt-Pt interaction at the excited state.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anthraquinones / chemistry*
  • Cross-Linking Reagents / chemistry*
  • Molecular Structure
  • Platinum Compounds / chemical synthesis*
  • Platinum Compounds / chemistry
  • Spectrophotometry
  • Time Factors

Substances

  • Anthraquinones
  • Cross-Linking Reagents
  • Platinum Compounds