Visualizing stepwise evolution of carbon hybridization from sp3 to sp2 and to sp

IF 14.7 1区 综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES
Wei Xiong, Guang Zhang, De-Liang Bao, Jianchen Lu, Lei Gao, Yusen Li, Hui Zhang, Zilin Ruan, Zhenliang Hao, Hong-Jun Gao, Long Chen, Jinming Cai
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Abstract

Regulating carbon hybridization states lies at the heart of engineering carbon materials with tailored properties but orchestrating the sequential transition across three states has remained elusive. Here, we visiualize stepwise evolution in carbon hybridizations from sp³ to sp² and to sp states via dehydrogenation and elimination reactions of methylcyano-functionalized molecules on surfaces. Utilizing scanning probing microscopy, we distinguish three distinct carbon-carbon bond types within polymers induced by annealing at elevated temperatures. Density-functional-theory calculations unveil the pivotal role of the electron-withdrawing cyano group in activating neighboring methylene to form C(sp3)–C(sp3) bonds, and in facilitating subsequent stepwise HCN eliminations to realize the transformation across three carbon-carbon bond types. We also demonstrate the applicability of this strategy on one-dimensional molecular wires and two-dimensional covalent organic framework on different substrates. Our work expands the scope of carbon hybridization evolution and serves as an advance in flexibly engineering carbon-material by employing cyanomethyl-substituted molecules.

Abstract Image

可视化碳杂化从 sp3 到 sp2 再到 sp 的逐步演变
调节碳杂化状态是工程碳材料定制性能的核心,但协调三个状态之间的顺序转变仍然是难以捉摸的。在这里,我们通过甲基氰基功能化分子在表面上的脱氢和消除反应,可视化了从sp³到sp²和sp态的碳杂化的逐步进化。利用扫描探针显微镜,我们在高温退火诱导的聚合物中区分出三种不同的碳碳键类型。密度泛函理论计算揭示了吸电子的氰基在激活邻近的亚甲基形成C(sp3) -C (sp3)键以及促进随后的HCN逐步消除以实现三种碳-碳键类型的转变方面的关键作用。我们还证明了该策略在不同底物上的一维分子线和二维共价有机框架上的适用性。我们的工作扩大了碳杂交进化的范围,并在利用氰甲基取代分子灵活工程碳材料方面取得了进展。
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来源期刊
Nature Communications
Nature Communications Biological Science Disciplines-
CiteScore
24.90
自引率
2.40%
发文量
6928
审稿时长
3.7 months
期刊介绍: Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.
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