Simultaneous Control of Pore‐Space Partition and Charge Distribution in Multi‐Modular Metal–Organic Frameworks. (13th February 2022)

• Record Type: Journal Article
• Authors: Hong, Anh N.; Kusumoputro, Emily; Wang, Yanxiang; Yang, Huajun; Chen, Yichong; Bu, Xianhui; Feng, Pingyun
• Is Part Of: Angewandte Chemie. Volume 134:Number 13(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-02-13
• Subjects: Anionic -- Gas Sorption -- MOFs -- Stability; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202116064
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: We report here a strategy for making anionic pacs type porous materials by combining pore space partition with charge reallocation. The method uses the first negatively charged pore partition ligand (2, 5, 8‐tri‐(4‐pyridyl)‐1, 3, 4, 6, 7, 9‐hexaazaphenalene, H‐tph) that simultaneously enables pore partition and charge reallocation. Over two dozen anionic pacs materials have been made to demonstrate their excellent chemical stability and a high degree of tunability. Notably, Ni3 ‐bdt‐tph (bdt=1, 4‐benzeneditetrazolate) exhibits month‐long water stability, while CoV‐bdt‐tph sets a new benchmark for C2 H2 storage capacity under ambient conditions for ionic MOFs. In addition to tunable in‐framework modules, we show feasibility to tune the type and concentration of extra‐framework counter cations and their influence on both stability and capability to separate industrial C3 H8 /C3 H6 and C6 H6 /C6 H12 mixtures. Abstract : Charge shifting via pore partition: A nine‐nitrogen ligand simultaneously enables pore‐space partition (via three N's) and charge reallocation (via six N's), thereby paving the way for multi‐modular assembly of a huge family of tunable anionic porous materials with much enhanced chemical stability and selective gas and vapor sorption.