近日，中国科学院大连化学物理研究所叶生发团队报道了用常规NiIV中心掺杂纳米石墨烯。2026年1月19日，《美国化学会志》发表了这一成果。

研究组通过将内消旋氧代取代的咔卟啉(1.1.1.0)单元引入六苯并晕苯骨架，合成了一种新型纳米石墨烯配体（化合物2）。该化合物具有adj-CCNN双阴离子核心，能与镍(II)阳离子配位形成有机镍(II)配合物3。值得注意的是，经X射线光电子能谱（XPS）与理论计算证实，配合物3在氯化铜处理后极易被氧化为形式上的镍(IV)物种4。配合物4在固态条件下表现出显著稳定性，但在室温下可与水快速反应，生成内氧插入型配合物5。

使用三氟乙酸对配合物5进行脱金属处理，最终获得含有醌型环结构的内氧掺杂游离碱6。研究组通过核磁共振波谱、单晶X射线衍射分析、紫外-可见-近红外光谱、循环伏安法以及密度泛函理论（DFT）计算，对新型含纳米石墨烯化合物2–6进行了全面表征与研究。据学界所知，配合物4是目前首例高活性镍(IV)纳米石墨烯配合物。该工作推动了纳米石墨烯金属掺杂化学的发展，进而为在纳米石墨烯碳网络内实现合成后杂原子掺杂开辟了新途径。

附：英文原文

Title: Doping a Nanographene with a Formal NiIV Center

Author: Zhaohui Zong, Haodan He, Mengdi Huang, Zhe Liu, Ningchao Liu, Shengfa Ye, Xian-Sheng Ke

Issue&Volume: January 19, 2026

Abstract: A new nanographene ligand (2) was synthesized by incorporating a meso-oxo substituted carbaporphyrin(1.1.1.0) unit into the hexa-peri-hexabenzocoronene (HBC) backbone. Compound 2 features an adj-CCNN dianionic core and coordinates with a NiII cation to form organo-NiII complex 3. Notably, complex 3 was readily oxidized to formal NiIV species 4 after treating with CuCl2, as confirmed with X-ray photoelectron spectroscopy (XPS) and theoretical calculations. Complex 4 showed substantial stability in the solid state but reacted rapidly with water at room temperature to yield inner oxygen-inserted complex 5. Demetalation of complex 5 with trifluoroacetic acid afforded an inner oxygen doped free base 6 containing a quinonoid-type ring. These new nanographene-containing compounds 2–6 were thoroughly characterized and studied using NMR spectroscopy, single-crystal X-ray diffraction analysis, UV–vis-NIR spectroscopy, and cyclic voltammetry as well as density functional theory (DFT) calculations. To the best of our knowledge, complex 4 represents the first example of a highly reactive NiIV nanographene complexes. The present work advances the development of metal doping chemistry of nanographenes, which in turn provide new access to postsynthetic heteroatom doping within the carbon networks of nanographenes.

DOI: 10.1021/jacs.5c18919

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c18919