Synthesis of Optically Active π-Conjugated Molecules Based on Planar Chiral [2.2]Paracyclophane

• Morisaki Yasuhiro

  Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University

• Chujo Yoshiki

  Kyoto University

Bibliographic Information

Other Title

• 面性不斉［2.2］パラシクロファンを基盤とする光学活性π共役系分子の合成
• メンセイ フセイ[2.2]パラシクロファン オ キバン ト スル コウガク カッセイpキョウヤクケイ ブンシ ノ ゴウセイ

Abstract

We have focused on planar chirality of [2.2]paracyclophanes with substituent(s). In addition, we have developed their practical optical resolution methods by mainly diastereomer methods and synthetic routes to planar chiral [2.2]paracyclophane compounds. The obtained optically active disubstituted and tetrasubstituted [2.2]paracyclophanes have been utilized for chiral building blocks to produce a wide variety of optically active π-stacked molecules including polymers. The planar chiral [2.2]paracyclophane-based π-stacked molecules exhibited circularly polarized luminescence (CPL) with a large dissymmetry factor (g_lum value) derived from the optically active second-ordered structures, such as V-, X-, triangle-, one-handed double helical structures, in the excited state. It was the first example on the application of the planar chirality of [2.2]paracyclophane to the field of polymer chemistry as well as materials chemistry. π-Electron systems constructed by [2.2]paracyclophane emit photoluminescence (PL) depending on the conjugation length of the stacked π-electron system. When conjugation length of a stacked π-electron system is extended, the molecule exhibits monomeric PL rather than excimer-like PL despite the stacked structure in proximity. Even if the several tens of π-electron systems are stacked, PL profiles such as PL life time and quantum efficiency are identical. π-Conjugation lengths of monomeric π-electron systems in this article are sufficiently extended; thus, the [2.2]paracyclophane-based π-stacked molecules in this article emit brightly with good PL quantum efficiencies. Moreover, the luminescence is CPL with the large g_lum value in organic molecules. It is quite difficult to achieve CPL with high brightness, high PL efficiency, and large g_lum value by using other scaffolds; therefore, planar chiral [2.2]paracyclophane is the ideal scaffold to be an excellent CPL emitters.

Journal

• Journal of Synthetic Organic Chemistry, Japan

  Journal of Synthetic Organic Chemistry, Japan 76 (10), 1055-1065, 2018-10-01

  The Society of Synthetic Organic Chemistry, Japan

Keywords

• [2.2]paracyclophane
• planar chirality
• π-conjugated compounds
• π-stacked compounds
• optical resolution
• circularly polarized luminescence

Details

• CRID: 1390282763051051136
• NII Article ID: 130007496491
• NII Book ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.76.1055
• ISSN: 18836526
• ISSN: 00379980
• NDL BIB ID: 029304481
• Web Site: http://id.ndl.go.jp/bib/029304481
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I029304481
• Web Site: https://www.jstage.jst.go.jp/article/yukigoseikyokaishi/76/10/76_1055/_pdf
• Text Lang: ja
• Data Source:
  • JaLC
  • NDL
  • Crossref
  • CiNii Articles
  • KAKEN
• Abstract License Flag: Disallowed