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A family of neutral cyclometalated platinum(II) complexes [(C^N)Pt(η‐S^S)] with π‐bonded benzenedithiolate {(η‐S^S) = Cp*Ru(C6H4S2)} and various cyclometalated ligands, {(C^N) = 2‐phenylpyridine (ppy), (2); 2,4‐difluorophenylpyridine (F2ppy) (3), benzo[h]quinoline (bzq) (4); dibenzo[f,h]quinoline (dbzq) (5)} were prepared and fully characterized. For comparison purposes the related bipyridine platinum(II) complex [(bpy)Pt(η‐S^S)][OTf] (6) was also prepared. The electrochemistry behavior of these complexes was investigated and shows the enhanced stability of these compounds toward oxidation due to the presence of Cp*Ru moiety which is now π‐bonded to the benzenedithiolato group. Moreover, several complexes were identified by single‐crystal X‐ray molecular structures. To the best of our knowledge, these are the first structures to be reported for cyclometalated platinum complexes with a π‐bonded benzenedithiolate (bdt) ligand. All of the complexes are luminescent in fluid solution at room temperature and in glassy solution at 77 K; their emission properties can be tuned through ligand variation. [ABSTRACT FROM AUTHOR]

A novel class of chiral luminescent square-planar platinum complexes with a π-bonded chiral thioquinonoid ligand is described. Remarkably the presence of this chiral organometallic ligand controls the aggregation of this square planar luminophor and imposes a homo- or hetero-chiral arrangement at the supramolecular level, displaying non-covalent Pt-Pt and π-π interactions. Interestingly these complexes are highly luminescent in the crystalline state and their photophysical properties can be traced to their aggregation in the solid state. A TD-DFT calculation is obtained to rationalize this unique behavior. [ABSTRACT FROM AUTHOR]

Two cycloplatinated complexes of the form [Pt(NC)CH3( P)]+ incorporating a rare, bidentate NC-chelating pyridylpyridylidene ligand are reported. The phosphorus-based ligand P is either 2,4,6-triphenylphosphinine or triphenylphosphine. These mononuclear complexes have been fully characterised in solution and by single-crystal X-ray diffraction analysis. UV/Vis absorption and photoluminescence spectroscopy studies reveal strong phosphorescence from the phosphinine compound at 77 K but no emission from its triphenylphosphine analogue. This contrasting behaviour can be traced to the π-acceptor ability of the phosphabenzene ring, as corroborated by electrochemical and time-dependent DFT (TD-DFT) calculations. [ABSTRACT FROM AUTHOR]

A unique class of neutral cyclometalated platinum(ii) complexes 2–4 with π-bonded benzenedithiolate are reported including two X-ray molecular structures. To the best of our knowledge these are the first structures to be reported for cyclometalated platinum complexes with a benzenedithiolate ligand. All of the complexes are luminescent in fluid solution at room temperature and in frozen solvent glasses at 77 K and their emission properties can be tuned through ligand variation. [ABSTRACT FROM AUTHOR]

The enantiomeric relationship of chiral luminescent square‐planar platinum complexes is confirmed by circular dichroism traces, as shown for the functionalized Pt(t‐Bu3terpy) chromophore. The chiral organometallic ligand controls the homochiral or heterochiral solid‐state aggregation through π–π and Pt–Pt interactions. These complexes are highly luminescent in the crystalline state; their photophysical properties arise from solid‐state aggregation. More information can be found in the Communication by V. W. W. Yam, H. Amouri et al. on page 8032 ff. [ABSTRACT FROM AUTHOR]