Synthesis and Electrochemistry of the Rhenium(I) Tricarbonyl Complexes of meso-Substituted [14]Tribenzotriphyrin(2.1.1)

Metalation of [14]tribenzotriphyrin(2.1.1) (TriP, 1a–d) with Re(CO)5Cl provides Re(I) tricarbonyl ReI-TriP complexes (2a–d) in 93–98% yields. The complexes were characterized by mass spectrometry, UV–Vis absorption and 1H NMR spectroscopy. Single crystal X-ray analyses reveals that 2b adopts dome-shaped conformation. The rhenium(I) ion is coordinated with three pyrrolic nitrogen atoms together with three carbonyl ligands. ReI-TriP (2a–d) complexes shown blue-shift absorption spectra which the Soret-band shifted to the region that around 390 nm. The redox properties of ReI-TriP (2a–d) were studied by cyclic voltammetry. Each compound undergoes one reversible one-electron oxidation and two reversible one-electron reductions in CH2Cl2.

Graphical abstractA series of rhenium(I) tricarbonyl complexes of [14]tribenzotriphyrin(2.1.1) have been successfully synthesized. The complexes were characterized by X-ray crystallography, 1H NMR spectroscopy and electrochemical measurements. The optical and redox properties and electronic structures were analyzed with theoretical calculations.Figure optionsDownload full-size imageDownload as PowerPoint slide