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.
J Am Chem Soc. 2022 Aug 24;144(33):15403-15410. doi: 10.1021/jacs.2c07480. Epub 2022 Aug 11.
Fabrication of uniform two-dimensional (2D) structures from small molecules remains a formidable challenge for living self-assembly despite its great success in producing uniform one-dimensional (1D) structures. Here, we report the construction of unprecedented uniform 2D platelets with tailorable shapes and controlled sizes by creating new nuclei from a donor-acceptor (D-A) molecule and 1-hexanol to initiate 2D living self-assembly. We demonstrate that the D-A molecule undergoes 1-hexanol-induced twisting to form continuous alternative hydrogen bonds in-between under electrostatic attraction, which in turn forms a new nucleus. This connection architecture of the new nucleus allows to simultaneously regulate the growth rate of in two dimensions to generate 2D platelets of distinct shapes through simply varying the amount of 1-hexanol relative to hexane. Furthermore, the living nature of the new nucleus enables seeded growth of complex concentric multiblock 2D heteroplatelets by sequential and alternative addition of different D-A molecules. Interestingly, the resulting 2D platelets obtained by such living self-assembly exhibit enhanced photostability compared to those obtained by conventional self-assembly without the involvement of 1-hexanol.
尽管小分子在一维（1D）结构的自组装中取得了巨大的成功，但要从小分子中构建均匀的二维（2D）结构仍然是一项艰巨的挑战。在这里，我们通过从供体-受体（D-A）分子和 1-己醇中创建新核来引发 2D 活自组装，报告了前所未有的具有可定制形状和受控尺寸的均匀 2D 薄片的构建。我们证明，D-A 分子在 1-己醇的诱导下发生扭曲，在静电吸引下在分子间形成连续的交替氢键，从而形成新核。这种新核的连接结构允许同时调节在二维方向上的生长速率，通过简单地改变相对于己烷的 1-己醇的量来生成具有不同形状的 2D 薄片。此外，新核的活性质使通过顺序和交替添加不同的 D-A 分子能够进行复杂的同心多嵌段 2D 异质薄片的种子生长。有趣的是，与没有涉及 1-己醇的常规自组装相比，通过这种活自组装获得的 2D 薄片表现出增强的光稳定性。
