兰州大学邵向锋报道了Cu催化脱氧偶联自底向上制备扭曲石墨烯纳米带。相关研究成果于2022年9月13日发表于国际一流学术期刊《德国应用化学》。
石墨烯纳米带（GNRs）在有机光电材料中有着广阔的应用前景，其性能在很大程度上取决于尺寸、边缘和构象。
该文中，从六丁氧基苯并菲方便地合成了长度高达2.65nm的全扶手边GNRs（AGNRs），其中铜催化脱氧偶联是关键步骤。所得的AGNRs（2HBT、3HBT和4HBT）具有高度扭曲的π-支架，并且相邻的苯并菲部分之间的扭转角大于32o，这通过晶体分析证明。理论和光谱研究表明，丁氧基赋予AGNRs富电子特征，π-系统从2HBT扩展到4HBT增强了S0→ S1激发和π-支架的畸变，提高了荧光量子产率（ФF）。特别是，4HBT具有最低的氧化电位（Eox 1=0.55 V vs.SCE），并显示出ФF为81%的红色荧光。
附：英文原文
Title: Bottom-Up Preparation of Twisted Graphene Nanoribbons via Cu-Catalyzed Deoxygenative Coupling
Author: Yuan Gao, Xinqiang Hua, Wei Jiang, Chun-Lin Sun, Chengshan Yuan, Zitong Liu, Hao-Li Zh, Xiangfeng Shao
Issue&Volume: 2022-09-13
Abstract: Graphene nanoribbons (GNRs) are promising in organic optoelectronic materials, and their properties largely depend on the size, edge, and conformation. Herein, the fully armchair-edged GNRs (AGNRs) with lengths up to 2.65 nm were conveniently synthesized from hexabutoxytriphenylene, where a Cu-catalyzed deoxygenative coupling was disclosed and served as a key step. The resulting AGNRs ( 2HBT , 3HBT , and 4HBT ) possess highly twisted π-scaffolds, and the torsion angles between the adjacent triphenylene moieties are larger than 32 o as proved by crystallographic analyses. Theoretical and spectroscopic studies manifest that butoxyls endow AGNRs with an electron-rich feature, the extension of the π-system from 2HBT to 4HBT reinforces S 0 → S 1 excitation, and the distortion of π-scaffold enhances fluorescence quantum yield ( Ф F ). Particularly, 4HBT has the lowest oxidation potential ( E ox 1 = 0.55 V vs. SCE) and displays red fluorescence with Ф F of 81%.
DOI: 10.1002/anie.202210924
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202210924
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