Nakashige Yuichi, Nakatsuji Hidefumi, Matsushima Kaho, Murakami Kazuo, Ito Hideto, Itami Kenichiro
Research Institute, Taoka Chemical Co., Ltd., 4-2-11 Nishhimikuni, Yodogawa-ku, Osaka 532-0006, Japan.
Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan.
Precis Chem. 2025 Apr 18;3(9):535-540. doi: 10.1021/prechem.5c00032. eCollection 2025 Sep 22.
Chrysene-based nanographenes (ChrNGs), despite their relatively small structures, have been reported to exhibit low highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps and strong long-wavelength fluorescence, making them attractive for various applications. However, the precise synthesis of ChrNGs remains challenging, and their availability is limited compared with other classes of nanographenes. Herein, we report the synthesis of novel ChrNGs by a successive annulative π-extension (APEX) reaction. Using diphenylacetylene and benzonaphthosilole in a Pd/-chloranil catalytic system, successive APEX afforded ChrNGs of various lengths and degrees of oxidation. Furthermore, exhaustive separation and further π-extension by cyclodehydrogenation afforded ChrNGs with more flat and rigid structures. Photophysical measurements of the obtained ChrNGs showed a variety of absorption and emission properties, including intense multicolor emission.
尽管基于屈的纳米石墨烯（ChrNGs）结构相对较小，但据报道它们具有较低的最高占据分子轨道（HOMO）-最低未占据分子轨道（LUMO）能隙和强烈的长波长荧光，这使得它们在各种应用中具有吸引力。然而，ChrNGs的精确合成仍然具有挑战性，并且与其他类别的纳米石墨烯相比，它们的可得性有限。在此，我们报道了通过连续累积π-扩展（APEX）反应合成新型ChrNGs。在Pd/四氯苯醌催化体系中使用二苯乙炔和苯并萘并硅杂环戊二烯，连续的APEX反应得到了各种长度和氧化程度的ChrNGs。此外，通过彻底分离和环脱氢进一步进行π-扩展，得到了结构更扁平、更刚性的ChrNGs。对所得ChrNGs的光物理测量显示出各种吸收和发射特性，包括强烈的多色发射。
