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The First Silicon(IV) Corrole Complexes: Synthesis, Structures, Properties, and Formation of a μ‐Oxo Dimer
Author(s) -
Ueta Kento,
Fukuda Masaya,
Kim Gakhyun,
Shimizu Soji,
Tanaka Takayuki,
Kim Dongho,
Osuka Atsuhiro
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800165
Subject(s) - corrole , chemistry , dimer , crystallography , atom (system on chip) , photochemistry , absorption (acoustics) , ultrafast laser spectroscopy , spectroscopy , materials science , physics , organic chemistry , quantum mechanics , computer science , composite material , embedded system
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 S 1 state. These intriguing optical properties have been comprehensively studied by magnetic circular dichroism (MCD) spectroscopy, femtosecond transient absorption (fs‐TA) measurements, and theoretical calculations.