Synthesis of Aza[<i>n</i>]helicenes up to <i>n</i> = 19: Hydrogen-Bond-Assisted Solubility and Benzannulation Strategy
-
- Yusuke Matsuo
- Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
-
- Masayuki Gon
- Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
-
- Kazuo Tanaka
- Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
-
- Shu Seki
- Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
-
- Takayuki Tanaka
- Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
書誌事項
- 公開日
- 2024-06-12
- 資源種別
- journal article
- 権利情報
-
- https://doi.org/10.15223/policy-029
- https://doi.org/10.15223/policy-037
- https://doi.org/10.15223/policy-045
- DOI
-
- 10.1021/jacs.4c05156
- 公開者
- American Chemical Society (ACS)
この論文をさがす
説明
Synthetic challenges toward anomalous structures and electronic states often involve handling problems such as insolubility in common organic solvents and oxidative degradation under aerobic conditions. We designed benzo-annulated aza[n]helicenes, which benefit from both the suppressed elevation of highest occupied molecular orbital (HOMO) energies and high solubility due to hydrogen bonding with solvent molecules to overcome these challenges. This strategy enabled the synthesis of six new aza[n]helicenes ([n]AHs) of different lengths (n = 9-19) from acyclic precursors via one-pot intramolecular oxidative fusion reactions. The structures of all of the synthesized aza[n]helicenes were determined by X-ray diffraction (XRD) analysis, and their electrochemical potentials were measured by cyclic voltammetry. Among the synthesized aza[n]helicenes, [17]AH and [19]AH are the first heterohelicenes with a triple-layered helix. The noncovalent interaction (NCI) plots confirm the existence of an effective π-π interaction between the layers. The absorption and fluorescence spectra red-shifted as the helical lengths increased, without any distinct saturation points. The optical resolutions of N-butylated [9]AH, [11]AH, [13]AH, and [15]AH were accomplished, and their circular dichroism (CD) and circularly polarized luminescence (CPL) were measured. Thus, the structural, (chir)optical, and electrochemical properties of the aza[n]helicenes were comprehensively analyzed.
収録刊行物
-
- Journal of the American Chemical Society
-
Journal of the American Chemical Society 146 (25), 17428-17437, 2024-06-12
American Chemical Society (ACS)