A Persistent Concealed Non-Kekulé Nanographene: Synthesis and in-situ Characterization

IF 4.6 1区化学 Q1 CHEMISTRY, ORGANIC Organic Chemistry Frontiers Pub Date : 2024-12-20 DOI:10.1039/d4qo02019g

Muhammad Imran, Lin Yang, Jinjiang Zhang, Yubin Fu, Zhen-Lin Qiu, Noel Israel, Evgenia Dmitrieva, Gianluca Serra, Andrea Lucotti, Matteo Tommasini, Ji Ma, Xinliang Feng

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Abstract

Concealed non-Kekulé (CNK) nanographenes have recently gained attention as promising non-Kekulé model systems due to their distinctive antiferromagnetic electronic spins, which offer potential applications in spintronics and quantum information science. However, synthesizing CNK nanographenes in solution remains a significant challenge because of their strong biradical character and high reactivity. In this study, we report the successful synthesis of a novel CNK nanographene with two phenalene units fused in a cis configuration to perylene (c-CNK), which exhibits persistent stability under ambient conditions, with a half-life (t1/2) of 59 minutes. The formation of the c-CNK is confirmed using in-situ UV-Vis-NIR spectroscopy, Raman spectroscopy, and high-resolution mass spectrometry. The open-shell character of c-CNK is supported by the electron paramagnetic resonance (EPR) spectroscopy by observing an isotropic signal with a g-value of 2.0026. Quantum chemical simulations reveal a high biradical character (y0 = 0.97) and a singlet open-shell ground state with a small singlet-triplet energy gap (ΔES-T) of 0.4 kcal/mol. This work presents a solution synthesis of a next-generation concealed non-Kekulé nanographene with intrinsic antiferromagnetic electronic spins, highlighting its potential as promising material for future quantum technologies.

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隐蔽非凯库勒（CNK）纳米石墨烯因其独特的反铁磁性电子自旋而成为前景广阔的非凯库勒模型系统，在自旋电子学和量子信息科学领域具有潜在的应用前景。然而，由于 CNK 纳米石墨烯具有强双极性和高反应性，因此在溶液中合成 CNK 纳米石墨烯仍然是一项重大挑战。在本研究中，我们报告了一种新型 CNK 纳米石墨烯的成功合成，其两个苯丙烯单元以顺式构型与过ylene（c-CNK）融合，在环境条件下表现出持久的稳定性，半衰期（t1/2）为 59 分钟。c-CNK 的形成是通过原位紫外-可见-近红外光谱、拉曼光谱和高分辨率质谱法证实的。电子顺磁共振（EPR）光谱通过观察 g 值为 2.0026 的各向同性信号，证实了 c-CNK 的开壳特性。量子化学模拟显示，该化合物具有较高的双极性（y0 = 0.97）和单线开壳基态，单线-三线能隙（ΔES-T）为 0.4 kcal/mol。这项研究提出了一种具有本征反铁磁性电子自旋的下一代隐蔽非凯库勒纳米石墨烯的溶液合成方法，凸显了它作为未来量子技术材料的潜力。

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来源期刊

Organic Chemistry Frontiers CHEMISTRY, ORGANIC-

CiteScore

7.90

自引率

11.10%

发文量

686

审稿时长

1 months

期刊介绍： Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.