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Cyclometalated heteronuclear Pt/Ag and Pt/Tl complexes: A structural and photophysical study

Dalton Transactions, ISSN: 1477-9226, Vol: 43, Issue: 3, Page: 1105-1116
2014
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Metrics Details

  • Citations
    24
    • Citation Indexes
      24
  • Captures
    20

Article Description

To investigate the factors influencing the luminescent properties of polymetallic cycloplatinated complexes a detailed study of the photophysical and structural properties of the heteronuclear complexes [PtMe (bhq)(μ-dppy)Ag(μ-acetone) ](BF), 2, [PtMe(bhq)(dppy)Tl]PF, 3, and [PtMe(bhq)(dppy)Tl]PF , 4, [bhq = benzo[h]quinoline, dppy = 2-(diphenylphosphino)pyridine] was conducted. Complexes 3 and 4 synthesized by the reaction of [PtMe(bhq)(dppy)], 1, with TlPF (1 or 1/2 equiv.) and stabilized by unsupported Pt-Tl bonds as revealed by multinuclear NMR spectroscopy and confirmed by X-ray crystallography for 3. DFT calculations for the previously reported butterfly PtAg cluster 2 reveal that in the optimized geometry the bridging acetone molecule is removed and the metal core displays a planar-shaped geometry in which according to a QTAIM calculation and natural bond orbital (NBO) analysis the Ag⋯Ag metallophilic interaction is strengthened. In contrast to the precursor 1, which is only emissive in glassy solutions (MLCT 485 nm), all 2-4 heteropolynuclear complexes display intense emissions in the solid state and in glassy solutions. Time-dependent density functional theory (TD-DFT) is used to elucidate the origin of the electronic transitions in the heteronuclear complexes 2 and 3. The low energy absorption and intense orange emission for cluster 2 (solid 77 K and glass) are attributed to metal-metal to ligand charge transfer (MM′LCT) with a minor L′LCT contribution. For 3 and 4 two different bands are developed: the high energy band (602-630 nm) observed for 4 at 77 K (solid, glass) and in diluted glasses for 3 is ascribed to emission from discrete PtTl units of mixed L′LCT/LM′CT origin. However, the low energy band (670-690 nm) observed at room temperature (solid) for both complexes and also in concentrated glasses for 3 is assigned to ππ excited states arising from intermolecular interactions. © The Royal Society of Chemistry 2014.

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