A Convenient Approach to Luminescent Cyclometalated Platinum(II) Complexes with Organometallic π‐Bonded Benzenedithiolate

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.