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

Qin, Jun-Sheng, Du, Dong-Ying, Li, Mian, Lian, Xi-Zhen, Dong, Long-Zhang, Bosch, Mathieu, Su, Zhong-Min, Zhang, Qiang, Li, Shun-Li, Lan, Ya-Qian, Yuan, Shuai, Zhou, Hong-Cai
Journal of the American Chemical Society 2016 v.138 no.16 pp. 5299-5307
biomimetics, catalysts, catalytic activity, coordination polymers, prediction, topology
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.