Derivation and Decoration of Nets with Trigonal-Prismatic Nodes: A Unique Route to Reticular Synthesis of Metal–Organic Frameworks

Quests for advanced functionalities in metal–organic frameworks (MOFs) inevitably encounter increasing complexity in their tailored framework architectures, accompanied by heightened challenges with their geometric design. In this paper, we demonstrate the feasibility of rationally exploiting topological prediction as a blueprint for predesigned MOFs. A new triangular frusta secondary building unit (SBU), {Zn4(tz)3}, was bridged by three TDC2– fragments to initially form a trigonal prismatic node, {Zn8(tz)6(TDC)3} (Htz = 1H-1,2,3-triazole and H2TDC = 2,5-thiophenedicarboxylic acid). Furthermore, the trigonal prism unit can be considered as a double SBU derived from triply bound triangular frusta. By considering theoretical derived nets for linking this trigonal-prismatic node with ditopic, tritopic, and tetratopic linkers, we have synthesized and characterized a new family of MOFs that adopt the decorated lon, jea, and xai nets, respectively. Pore sizes have also been successively increased within TPMOF-n family, which facilitates heterogeneous biomimetic catalysis with Fe–porphyrin-based TPMOF-7 as a catalyst.

金属有机框架（metal–organic frameworks, MOFs）的高级功能研发需求，不可避免地伴随着定制化框架结构复杂度的提升，以及几何设计难度的显著增加。本文论证了将拓扑预测作为预设计MOFs理性化蓝图的可行性。本研究通过三条TDC²⁻片段桥联新型三角台状次级结构单元（secondary building unit, SBU）{Zn₄(tz)₃}，初步构筑得到三角棱柱型节点{Zn₈(tz)₆(TDC)₃}（其中Htz代表1H-1,2,3-三唑，H₂TDC代表2,5-噻吩二羧酸）。进一步分析表明，该三角棱柱单元可视为由三重键合三角台状结构衍生得到的双次级结构单元。通过结合理论推导的拓扑网络，将该三角棱柱节点与双连接位点、三连接位点及四连接位点连接配体进行组装，我们成功合成并表征了一系列新型MOFs材料，它们分别对应修饰型lon、jea及xai拓扑网络。TPMOF-n系列材料的孔径依次递增，该特性为以铁卟啉基TPMOF-7为催化剂的非均相仿生催化反应提供了有利条件。