Alkynylphosphonium Pt(II) Complexes: Synthesis, Characterization, and Features of Photophysical Properties in Solution and in the Solid State.

A series of heteroleptic bis-alkynyl-diimine mononuclear Pt(II) complexes with alkynylphosphonium and di- tert -butyl-2,2'-bipyridine (dtbpy) ligands have been prepared and characterized by spectroscopic methods and single-crystal XRD. The Pt(II) complexes obtained in the present study demonstrate triplet emission in solution, which originates from 3 MLCT/ 3 LC states where the nature of the π-conjugated linker in the alkynylphosphonium ligand manages the contributions of each transition, and this conclusion is supported by DFT calculations. Additionally, the presence of the phosphonium group connected to alkynyl through the π-conjugated linker enhances nonlinear optical properties of the Pt(II) complexes increasing two-photon absorption cross section up to 400 GM. In the solid state, the Pt(II) complexes demonstrate emission that is attributed to 3 MMLCT transitions due to the presence of Pt-Pt metallophilic interactions, and the reversible assembly and disassembly of these interactions by grinding and solvent treatment are responsible for the mechanochromic luminescence. It has been experimentally shown that stimuli-responsive emission of the Pt(II) complexes is the result of a "monomer/dimer" transformation; this conclusion is confirmed by DFT calculations for discrete complexes and different dimers with or without Pt-Pt interactions.