A persistent concealed non-Kekulé nanographene: synthesis and in situ characterization,Organic Chemistry Frontiers

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A persistent concealed non-Kekulé nanographene: synthesis and in situ characterization
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2024-12-20 , DOI: 10.1039/d4qo02019g
Muhammad Imran _{1,

2} , Lin Yang _{1,

2} , Jin-Jiang Zhang ₂ , Zhen-Lin Qiu ₁ , Yubin Fu _{1,

2} , Noel Israel ₃ , Evgenia Dmitrieva ₃ , Andrea Lucotti ₄ , Gianluca Serra ₄ , Matteo Tommasini ₄ , Ji Ma ₅ , Xinliang Feng _{1,

2}

Affiliation

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 (t_1/2) of 59 minutes. The formation of 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 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 (ΔE_S–T) of 0.4 kcal mol⁻¹. This work presents a solution synthesis of a next-generation concealed non-Kekulé nanographene with intrinsic antiferromagnetic electronic spins, highlighting its potential as a promising material for future quantum technologies.

中文翻译：

一种持久性隐藏的非 Kekulé 纳米石墨烯：合成和原位表征

隐藏的非凯库勒（CNK）纳米石墨烯因其独特的反铁磁电子自旋而作为有前途的非凯库勒模型系统而受到关注，这在自旋电子学和量子信息科学中提供了潜在的应用。然而，由于CNK纳米石墨烯具有很强的双自由基特性和高反应性，因此在溶液中合成CNK纳米石墨烯仍然是一个重大挑战。在这项研究中，我们报道了一种新型 CNK 纳米石墨烯的成功合成，其中两个苯单元以顺式构型熔融成苝（c-CNK），它在环境条件下表现出持久的稳定性，半衰期（t_1/2）为 59 分钟。使用原位 UV-Vis-NIR 光谱、拉曼光谱和高分辨率质谱证实 c-CNK 的形成。电子顺磁共振（EPR）波谱通过观察 g 值为 2.0026 的各向同性信号来支持 c-CNK 的开壳层特性。量子化学模拟揭示了高双自由基特性（y₀ = 0.97）和单重态开壳基态，具有 0.4 kcal ^mol-1 的小单重态-三重态能隙（ΔE_S–T）。这项工作提出了一种具有本征反铁磁电子自旋的下一代隐藏非 Kekulé 纳米石墨烯的溶液合成，突出了其作为未来量子技术有前途的材料的潜力。

更新日期：2024-12-20

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