Doubly Bonded Silicon Compounds Showing Intramolecular Charge-Transfer Transitions

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

Recent study of doubly bonded silicon compounds showing intramolecular charge-transfer transition was reviewed. Trialkylaryldisilenes having 1-naphthyl, 9-phenanthyl, or 9-anthryl substituent were synthesized. X-ray diffraction analysis shows that π(Si=Si) and π(aryl) systems in the trialkylaryldisilenes are almost perpendicular to each other suggesting no significant conjugative interactions between two π systems, but they exhibit intramolecular charge-transfer (ICT) transitions from π(Si=Si) to π*(aryl). Especially, 9-anthryltrialkyldisilene shows a distinct ICT band at 525nm, which redshifts to 535nm in more polar 1,2-dichlorobenzene. Reaction of the anthryldisilene gives the corresponding [2 + 1] cycloadduct, disilacyclopropanimine, which undergoes further isomerization to give 3-silylene-2-silaaziridine with 9-anthryl substituent as a novel exocyclic silene. The anthrylsilene shows also a distinct ICT transition from π(Si=C) to π*(aryl). The high energy levels of π(Si=Si) and π(Si=C) and the low-lying π*(aryl) would be responsible for the distinct ICT band of the disilenes and the silene.

Original languageEnglish
Title of host publicationChemical Science of Electron Systems
PublisherSpringer Japan
Pages379-391
Number of pages13
ISBN (Electronic)9784431553571
ISBN (Print)9784431553564
DOIs
Publication statusPublished - 2015 Jan 1

Keywords

  • Disilene
  • Intramolecular charge transfer
  • Silene
  • π-electron system

ASJC Scopus subject areas

  • Chemistry(all)
  • Engineering(all)
  • Biochemistry, Genetics and Molecular Biology(all)

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