Liang Kejiang, Liang Yimin, Tang Min, Liu Jiali, Tang Zheng-Bin, Liu Zhichang
Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province. Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, and Westlake Institute for Advanced Study, 600 Dunyu Road, Hangzhou, Zhejiang, 310030, China.
International Institute for Sustainability with Knotted Chiral Meta Matter, Hiroshima University, Higashihiroshima, Japan.
Angew Chem Int Ed Engl. 2024 Sep 16;63(38):e202409507. doi: 10.1002/anie.202409507. Epub 2024 Aug 19.
Modulating the arrangement of superstructures through noncovalent interactions has a significant impact on macroscopic shape and the expression of unique properties. Constructing π-interaction-driven hierarchical three-dimensional (3D) superstructures poses challenges on account of limited directional control and weak intermolecular interactions. Here we report the construction of a 3D diamondoid superstructure, named π-Diamond, employing a ditopic strained Z-shaped building block comprising a porphyrin unit as bow-limb double-strapped with two m-xylylene units as bowstrings. This superstructure, reminiscent of diamond's tetrahedral carbon composition, is composed of double-walled tetrahedron (DWT) driven solely by π-interactions. Hetero-π-stacking interactions between porphyrin and m-xylylene panels drive the assembly of four building blocks predominantly into a DWT, which undergoes extension to create an adamantane unit and eventually a diamondoid superstructure wherein each porphyrin panel is shared by two neighboring tetrahedra through hetero-π-stacking. π-Diamond exhibits a solid-state fluorescent quantum yield 44 times higher than that of tetraphenylporphyrin along with excellent photocatalytic performance. The precise 3D directionality of π-interactions, achieved through strained multipanel building blocks, revolutionizes the assembly of hierarchical 3D superstructures driven by π-interactions.
通过非共价相互作用调节超结构的排列对宏观形状和独特性质的表达具有重大影响。由于有限的方向控制和弱分子间相互作用，构建π相互作用驱动的分层三维（3D）超结构面临挑战。在此，我们报告了一种3D类金刚石超结构的构建，名为π-金刚石，它采用了一种双位点应变Z形构建单元，该单元包含一个卟啉单元作为弓臂，由两个间二甲苯单元作为弓弦进行双带连接。这种超结构让人联想到金刚石的四面体碳组成，它由仅由π相互作用驱动的双壁四面体（DWT）组成。卟啉和间二甲苯面板之间的异质π堆积相互作用驱动四个构建单元主要组装成一个DWT，该DWT经过扩展形成一个金刚烷单元，最终形成一个类金刚石超结构，其中每个卟啉面板通过异质π堆积被两个相邻四面体共享。π-金刚石的固态荧光量子产率比四苯基卟啉高44倍，同时具有优异的光催化性能。通过应变多面板构建单元实现的π相互作用的精确3D方向性，彻底改变了由π相互作用驱动的分层3D超结构的组装。
