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Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network, X‐pcu‐5‐Zn, by Pillar‐Ligand Substitution
Author(s) -
Zhu AiXin,
Yang QingYuan,
Mukherjee Soumya,
Kumar Amrit,
Deng ChengHua,
Bezrukov Andrey A.,
Shivanna Mohana,
Zaworotko Michael J.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201909977
Subject(s) - linker , acetylene , chemistry , substitution (logic) , ligand (biochemistry) , topology (electrical circuits) , adsorption , nanotechnology , materials science , organic chemistry , computer science , electrical engineering , receptor , biochemistry , programming language , engineering , operating system
Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu ‐topology MOF, X‐pcu‐5‐Zn , have been prepared: X‐pcu‐6‐Zn , 6 =1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn , 7 =1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn , 8 =4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N 2 , CO 2 , C 2 H 2 , and C 2 H 4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6 , afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.