화학공학소재연구정보센터
Inorganic Chemistry, Vol.46, No.26, 11291-11296, 2007
Synthesis of pendant-type anthraquinone-bridged cofacial dinuclear platinum(II) complexes and their emission properties
Anthraquinone-bridged mononuclear and dinuclear complexes, [PtCl(AQ-amide-tpy)](PF6) (1), [Pt2Cl2(AQ-amide-tpy(2))](PF6)(2) (2), and [Pt2Cl2(AQ-eth-tpy(2))](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 (c = similar to 1100 M-1 cm(-1)) in addition to an (MLCT)-M-1 absorption, which was ascribed to a (MILCT)-M-3 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.