Two is Better Than One? Investigating the Effect of Incorporating Re(CO)₃Cl Side-Chains into Pt(II) Diynes and Polyynes

Pt(II) di-ynes and poly-ynes incorporating 5,5’- and 6,6’-disubstituted 2,2’-bipyridines were prepared following conventional Sonogashira and Hagihara dehydrohalogenation reaction protocols. Using Pt(II) dimers and polymers as a rigid-rod backbone, four new hetero-bimetallic compounds incorporating Re(CO)3Cl as a pendant functionality in the 2,2’-bipyridine core were obtained. The new hetero-bimetallic Pt-Re compounds were characterized by analytical and spectroscopic techniques. The solid state structures of a Re(I)-coordinated diterminal alkynyl ligand and a representative model compound were determined by single-crystal X-ray diffraction. Detailed photo-physical characterization of the hetero-bimetallic Pt(II) di-ynes and poly-ynes was carried out. We find that the incorporation of the Re(CO)3Cl pendant functionality in the 2,2’-bipyridine-containing main-chain Pt(II) di-ynes and poly-ynes has a synergistic effect on the optical properties, red shifting the absorption profile and introducing strong long-wavelength absorptions. The Re(I) moiety also introduces strong emission into the monomeric Pt(II) di-yne compounds, whereas this is suppressed in the poly-ynes. The extent of the synergy depends on the topology of the ligands. Computational modelling was performed to compare the energetic stabilities of the positional isomers and to understand the microscopic origin of the major optical absorptions. We find that 5,5’-disubstituted 2,2’-bipyridine systems are better candidates in terms of yield, photophysical properties and stability than their 6,6’-substituted counterparts. Overall, this work provides an additional synthetic route to control the photo-physical properties of metalla-ynes for a variety of optoelectronic applications.