Liao Chenglong, Gong Yanjun, Che Yanxue, Cui Linfeng, Liu Yangxin, Ji Hongwei, Zhang Yifan, Zang Ling, Zhao Jincai, Che Yanke
Key Laboratory of Photochemistry CAS Research/Education Center for Excellence in Molecular Sciences Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Chemistry. 2023 Dec 22;29(72):e202301747. doi: 10.1002/chem.202301747. Epub 2023 Nov 7.
This study reports the design of a donor-acceptor (D-A) molecule with two fluorene units on each side of a benzothiadiazole moiety, which allows multiple intermolecular interactions to compete with one another so as to induce the evolution of the metastable 2D platelets to the stable 2D platelets during the self-assembly of the D-A molecule. Importantly, the living seeded self-assembly of metastable and stable 2D structures with precisely controlled sizes can be conveniently achieved using an appropriate supersaturated level of a solution of the D-A molecule as the seeded growth medium that can temporarily hold the almost-proceeding spontaneous nucleation from competing with the seeded growth. The stable 2D platelets with smaller area sizes exhibit higher sensitivity to gaseous dimethyl sulfide, illustrating that the novel living self-assembly method provides more available functional structures with controlled sizes for practical applications. The key finding of this study is that the new living methodology is separated into two independent processes: the elaborate molecular design for various crystalline structures as seeds and the application of a supersaturated solution with appropriate levels as the growth medium to grow the uniform structures with controlled sizes; this would make convenient and possible the living seeded self-assembly of rich 1D, 2D, and 3D architectures.
本研究报道了一种供体-受体（D-A）分子的设计，该分子在苯并噻二唑部分的两侧各有两个芴单元，这使得多种分子间相互作用能够相互竞争，从而在D-A分子的自组装过程中诱导亚稳二维血小板向稳定二维血小板的演化。重要的是，使用D-A分子溶液的适当过饱和水平作为种子生长介质，可以方便地实现尺寸精确可控的亚稳和稳定二维结构的活性种子自组装，该介质可以暂时阻止几乎正在进行的自发成核与种子生长竞争。面积尺寸较小的稳定二维血小板对气态二甲基硫表现出更高的敏感性，这表明这种新型的活性自组装方法为实际应用提供了更多尺寸可控的可用功能结构。本研究的关键发现是，新的活性方法分为两个独立的过程：针对各种晶体结构作为种子进行精细的分子设计，以及应用适当过饱和水平的溶液作为生长介质来生长尺寸可控的均匀结构；这将使丰富的一维、二维和三维结构的活性种子自组装变得方便且可行。
