Synthesis and Characterization of Dithia[3.3]metaparacyclophane‐Bridged Dimetallic Ruthenium Acetylide Complexes

Abstract

AbstractFour dithia[3.3]metaparacyclophane‐bridged dimetallic ruthenium acetylide complexes (1–4), in which the cyclophane units exhibit characteristic edge‐to‐face interactions between the top and bottom aromatic decks, have been designed, synthesized, and structurally characterized. X‐ray diffraction analysis of 1–3 revealed that effective edge‐to‐face interactions exist in the solid state. IR spectroelectrochemical results suggest that the dithia[3.3]metaparacyclophane bridging ligands are redox‐noninnocent. The UV/Vis/NIR spectra of 1+, 2+, 3+, and 4+ display characteristic band envelopes, and the deconvoluted multiple transitions have been assigned with the aid of DFT calculations to combinations of metal‐to‐ligand charge transfer (MLCT) and ligand‐to‐ligand charge transfer (LLCT) with appreciable contributions from transannular π–π transitions, especially for 3+ and 4+.