Dioxacyclophanes as a Scaffold for Silicon-based Circularly Polarized Luminescent Materials. Issue 16 (18th April 2019)

• Record Type: Journal Article
• Authors: Yamanoi, Yoshinori; Usuki, Tsukasa; Omoto, Kenichiro; Shimada, Masaki; Koike, Hikaru; Iwamura, Munetaka; Nozaki, Koichi; Saito, Daisuke; Kato, Masako; Nishihara, Hiroshi
• Is Part Of: Tetrahedron letters. Volume 60:Issue 16(2019)
• Page Start: 1108
• Page End: 1112
• Publication Date: 2019-04-18
• Subjects: Dioxacyclophane -- Organosilane compounds -- Luminescence -- Circularly polarized luminescence (CPL); Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2019.03.033
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: Planar chiral organosilanes were prepared from dioxacyclophane as a building block. Absolute configurations were determined by single-crystal X-ray analysis. (+)-( R )-2 exhibited circularly polarized luminescence for a small organic molecule. Abstract: Planar chiral dioxacyclophanes were designed and synthesized as a key scaffold for materials with circularly polarized luminescence (CPL). Representative planar chiral 1, 12-dioxa[12](1, 4)naphthaleneophane-derived organosilane compounds (−)-( R )-1, (+)-( R )-2, and (−)-( R )-3 were prepared by (+)-sparteine-mediated aryl metalation and an electrophilic reaction with chlorosilanes. The absolute configurations of the planar chirality were determined in the R form by single-crystal X-ray analysis. Optically active compound (+)-( R )-2 exhibited blue fluorescence and a CPL signal with a dissymmetry factor ( g lum value) of 0.001 in solution. The electronic structure was corroborated by DFT and TD-DFT calculations rationalizing the observed spectroscopic properties.