Tai Wenjun, Sun Lishan, Liu Shuya, Hu Qiongzheng, Yu Li, Che Yanke, Gong Yanjun, Zhao Jincai
Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan, China.
Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
Nat Commun. 2025 Aug 26;16(1):7968. doi: 10.1038/s41467-025-63336-y.
Defect engineering plays a pivotal role in materials science, as defects significantly influence material properties. However, achieving precise control over defects in pure organic systems remains a challenge. In this study, we demonstrate the creation of controllable defects in molecular crystals through supersaturated solution-fed seeded self-assembly of two strategically designed molecules. One molecule features 2-(2'-hydroxyphenyl)benzimidazole groups at both ends, enabling the formation of an intramolecular hydrogen bond on one side while leaving the hydrogen bond donors on the other side available for potential intermolecular interactions. When coassembled with a second molecule containing benzimidazole groups capable of continuous intermolecular hydrogen bonding, defects in the hydrogen-bonding network are introduced, resulting in the formation of defects within the resulting two-dimensional cocrystals. The defect density can be precisely tuned by adjusting the molar ratio of the two molecules. Remarkably, these defects exhibit shape-complementary hydrogen bonding with dimethoate enabling high sensitivity and selectivity molecular recognition.
缺陷工程在材料科学中起着关键作用，因为缺陷会显著影响材料性能。然而，在纯有机体系中实现对缺陷的精确控制仍然是一项挑战。在本研究中，我们展示了通过两种精心设计的分子的过饱和溶液进料晶种自组装，在分子晶体中创建可控缺陷。一种分子两端具有2-(2'-羟基苯基)苯并咪唑基团，使得一侧能够形成分子内氢键，而另一侧的氢键供体可用于潜在的分子间相互作用。当与第二种含有能够形成连续分子间氢键的苯并咪唑基团的分子共组装时，氢键网络中会引入缺陷，从而在所得的二维共晶体中形成缺陷。通过调整两种分子的摩尔比可以精确调节缺陷密度。值得注意的是，这些缺陷与乐果呈现形状互补的氢键作用，从而实现高灵敏度和选择性的分子识别。
