Platinum(II)-Substituted Phenylacetylide Complexes Supported by Acyclic Diaminocarbene Ligands

We introduce phosphorescent platinum aryl acetylide complexes supported by tert-butyl-isocyanide and strongly σ-donating acyclic diaminocarbene (ADC) ligands. The precursor complexes cis-[Pt(CNtBu)₂(C≡CAr)₂] (4a-4f) are treated with diethylamine, which undergoes nucleophilic addition with one of the isocyanides to form the cis-[Pt(CNtBu)(ADC)(C≡CAr)₂] complexes (5a-5f). The new compounds incorporate either electron-donating groups (4-OMe and 4-NMe₂) or electron-withdrawing groups [3,5-(OMe)₂, 3,5-(CF₃)₂, 4-CN, and 4-NO₂] on the aryl acetylide. Experimental HOMO-LUMO gaps, estimated from cyclic voltammetry, span the range of 2.68-3.61 eV and are in most cases smaller than the unsubstituted parent complex, as corroborated by DFT. In the ADC complexes, peak photoluminescence wavelengths span the range of 428 nm (2a, unsubstituted phenylacetylide) to 525 nm (5f, 4-NO₂-substituted), with the substituents inducing a red shift in all cases. The phosphorescence E_0,0 values and electrochemical HOMO-LUMO gaps are loosely correlated, showing that both can be reduced by either electron-donating or electron-withdrawing substituents on the aryl acetylides. The photoluminescence quantum yields in the ADC complexes are between 0.044 and 0.31 and the lifetimes are between 4.8 and 14 μs, a factor of 1.8-10× higher (for Φ_PL) and 1.2-3.6× longer (for τ) than the respective isocyanide precursor (Φ_PL = 0.014-0.12, τ = 2.8-8.2 μs).