Growth of covalent organic frameworks (COFs) as single crystals is extremely challenging. Inaccessibility of open‐structured single‐crystal COFs prevents the exploration of structure‐oriented applications. Herein we report for the first time a non‐interpenetrated single‐crystal COF, LZU‐306, which possesses the open structure constructed exclusively via covalent assembly. With a high void volume of 80 %, LZU‐306 was applied to investigate the intrinsic dynamics of reticulated tetraphenylethylene (TPE) as the individual aggregation‐induced‐emission moiety. Solid‐state ²H NMR investigation has determined that the rotation of benzene rings in TPE, being the freest among the reported cases, is as fast as 1.0×10⁴ Hz at 203 K to 1.5×10⁷ Hz at 293 K. This research not only explores a new paradigm for single‐crystal growth of open frameworks, but also provides a unique matrix‐isolation platform to reticulate functional moieties into a well‐defined and isolated state.

中文翻译：

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非互穿单晶共价有机框架。

共价有机骨架（COF）作为单晶的生长极具挑战性。开放结构的单晶COF的不可访问性阻止了对面向结构的应用程序的探索。在这里，我们首次报告了一种非互穿的单晶COF LZU-306，它具有仅通过共价组装构造的开放结构。LZU-306具有80％的高空隙体积，用于研究网状四苯乙烯（TPE）作为单个聚集诱导的发射部分的内在动力学。固态² H NMR研究确定，在报告的病例中，TPE中苯环的旋转是最自由的， 在203 K时旋转至1.0×10 ⁴ Hz至1.5×10 ⁷ Hz在293 K时的水平。这项研究不仅探索了开放框架单晶生长的新范例，而且还提供了一个独特的基质分离平台，可以将功能性部分网状化为定义明确和分离的状态。