Synthesis and π-Hole vs. π Effects of Pt(II) Complexes with Pentafluorophenyl and Phenyl-Substituted Bipyridines

Abstract

Four types of perfluoroarene-substituted and the corresponding non-fluorinated Pt(II) complexes, [PtCl2L] (L = 1 and 2), were prepared with 4,4′-bis(pentafluorophenyl)-2,2′-bipyridine (1a), 4,4′-diphenyl-2,2′-bipyridine (1b), 4,4′-bis(2-pentafluorophenylethynyl)-2,2′-bipyridine (2a), and 4,4′-bis(2-phenylethynyl)-2,2′-bipyridine (2b), respectively, to understand the role of perfluoroaromatic substitution and acetylene linkers on molecular structures and their induced supramolecular associations. The pentafluorophenyl groups lead to significant changes in electron distribution within the Pt(II) complexes, notably causing absorption bands to red-shift due to a metal-to-ligand charge transfer from nucleophilic platinum ions and demonstrating stabilization effects on the bands by fluorination in experimental and theoretical studies. The results of altering electron density and reducing the metal’s nucleophilic tendencies through fluorination and the use of an acetylene linker are discussed, accompanied by crystal structures, the corresponding Hirshfeld surface analysis, and DFT calculations.