A Platinum(II) Organometallic Building Block for the Design of Emissive Copper(I) and Silver(I) Coordination Polymers.

The tritopic organometallic ligand -MeSCHC≡CPt(PMe)(C≡N) () was prepared from -PtCl(PMe) and -ethynyl(methyl thioether)benzene. Its versatility was shown with the formation of [CuX()] coordination polymers (CPs) with CuX salts in MeCN (X = I (), CN (), SCN ()). These CPs were characterized by X-ray crystallography, thermal gravimetric analysis (TGA), and IR and Raman spectroscopy. consists of a 1D head-to-tail chain formed by tricoordinated -C≡N-CuI(η-C≡C)- linkages, whereas is built upon a central (CuCN) zigzag chain bearing dangling s held by -C≡N-Cu bonds. Finally, exhibits 2D sheets secured by Cu-N≡C-/-(Me)S-Cu bondings and transversal Cu-S-C≡N-Cu bridges. Concurrently, the CPs formed with AgX (X = NO ( and ), CFCO () PF ()) exhibits 2D sheets with guest molecules (anion, solvents) inside the tight pores or between layers. These new materials are emissive: (λ ∼465 nm), - (500 < λ < 620 nm). Their photophysical properties (absorption and emission spectra, emission lifetimes (∼0.2 < τ < 120 μs), and quantum yields in the solid state at 77 and 298 K) were analyzed. The various natures of the emissive excited states were addressed by density functional theory (DFT) and time-dependent DFT (TDDFT) computations. For , this state is a triplet halide or pseudohalide to ligand charge transfer XLCT (CT = charge transfer; X = I; L = ) and for , it is XLCT (X = CN; L = ). However, for , it is XLCT (X = SCN; L = ). For , the T state is described as a [MeSCH(η-C≡C)-Ag(NO)] → /C≡CCHSMe CT.