The synthesis of 3D covalent organic frameworks (COFs) adopting novel topologies is challenging, and so far 3D COFs have only been reported for nets based on building blocks with tetrahedral geometry. We demonstrate the targeted synthesis of an anionic 3D COF crystallizing in a three-coordinated srs net by exploiting a recently developed linkage for the formation of anionic silicate COFs based on hypercoordinate silicon nodes. The framework, named SiCOF-5, was synthesized by reticulating dianionic hexacoordinate [SiO6]2- nodes with triangular triphenylene building blocks and adopts a two-fold interpenetrated srs-c net with an overall composition of Na2[Si(C18H6O6)] (where C18H6O6 is triphenylene-2,3,6,7,10,11-hexakis(olate)). A key requirement for the crystallization of SiCOF-5 was the careful control over the nucleation and growth rate by gradual generation of the silicon source during the course of the reaction.

中文翻译：

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具有 srs 拓扑结构的 3D 阴离子硅酸盐共价有机框架

采用新型拓扑结构的 3D 共价有机框架 (COF) 的合成具有挑战性，到目前为止，仅针对基于具有四面体几何结构的构建块的网络报道了 3D COF。我们通过利用最近开发的基于超配位硅节点形成阴离子硅酸盐 COF 的联系，展示了在三配位 srs 网中结晶的阴离子 3D COF 的靶向合成。该骨架名为 SiCOF-5，是通过将双阴离子六配位 [SiO6]2- 节点与三角形苯并亚结构单元网状化而合成的，并采用整体组成为 Na2[Si(C18H6O6)] 的双层互穿 srs-c 网（其中C18H6O6 是三亚苯基-2,3,6,7,10,11-hexakis(olate))。