具有大共轭π面的非平面纳米石墨烯

本期文章：《美国化学会志》：Online/在线发表

中山大学王娇炳团队报道了具有大共轭π面的非平面纳米石墨烯。相关研究成果发表在2024年8月21日出版的《美国化学会杂志》。

共轭π表面在分子和材料中普遍存在。然而，尺寸高达几纳米的大π表面很难以原子精确的方式构建。由于强烈的π-π相互作用，它们倾向于聚集，导致纯化和光谱研究出现臭名昭著的问题。

相比之下，该文中研究人员报告了具有大、精确和无支撑的π表面的非平面纳米石墨烯1的设计、合成和完整表征。它可溶于常见的有机溶剂，可以进行彻底的研究。单晶X射线衍射明确证实了1的结构，该结构由85个稠环组成，π表面尺寸为3nm。

研究展示了不同寻常的电子结构、创纪录的高近红外吸收、明显的磁屏蔽和超强的异分子范德华复合物，使人们能够建立一种清晰的结构-性质关系。

研究结果对于研究和理解与离散和相互作用π表面相关的各种现象和过程具有广泛的意义。

附：英文原文

Title: Nonplanar Nanographene with a Large Conjugated π-Surface

Author: Zongchi Zhang, Han Zhu, Jiajian Gu, Haonan Shi, Takashi Hirose, Long Jiang, Yanpeng Zhu, Dingyong Zhong, Jiaobing Wang

Issue&Volume: August 21, 2024

Abstract: Conjugated π-surfaces are ubiquitous in molecules and materials. However, large π-surfaces up to a few nanometers in size are difficult to construct in an atomically precise manner. They tend to aggregate because of strong π–π interactions, resulting in notorious problems for both purification and spectroscopic investigations. Here, by contrast, we report the design, synthesis, and full characterizations of a nonplanar nanographene 1, which has a large, precise, and nonstacked π-surface. It is soluble in common organic solvents and allows for thorough investigations. The structure of 1, comprising 85 fused rings with an extended π-surface of 3 nm in size, is unambiguously confirmed by single-crystal X-ray diffraction. Unusual electronic structures, record-high near-infrared absorption, pronounced magnetic shielding, and ultrastrong heteromolecular van der Waals complexations are demonstrated, enabling us to establish a clear structure–property relationship, which has been elusive for decades. These results have broad implications for studying and understanding various phenomena and processes relevant to both discrete and interacting π-surfaces.

DOI: 10.1021/jacs.4c09167

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c09167