The First Silicon(IV) Corrole Complexes: Synthesis, Structures, Properties, and Formation of a μ-Oxo Dimer

Abstract

The first Si^IV corrole complexes were synthesized in good yields by treatment of meso-triarylcorroles with tetrachlorosilane in 1,2-dichloroethane at 60 °C. The central silicon atom possesses a square-pyramidal coordination geometry with slightly longer Si-N bond lengths as compared with those of known triazacorrole Si^IV complexes. The Si^IV corrole complexes exhibit sharp and blue-shifted absorption spectra and larger fluorescence quantum yields as compared with the corresponding free-base corroles. A μ-oxo dimer of a Si^IV corrole was synthesized upon treatment with methanesulfonyl chloride in pyridine at 100 °C. This dimer shows a face-to-face structure with a 90° twist in the solid state. Although the dimer exhibits a blue-shifted Soret band, reflecting the face-to-face geometry, it displays a largely red-shifted and broad fluorescence spectrum with a large Stokes shift, suggesting a large structural change in the S₁ state. These intriguing optical properties have been comprehensively studied by magnetic circular dichroism (MCD) spectroscopy, femtosecond transient absorption (fs-TA) measurements, and theoretical calculations.

Keywords: X-ray diffraction analysis; excited-state dynamics; fluorescence spectroscopy; porphyrinoids; silicon.