Influence of Co-adsorbates on CO₂ induced phase transition in functionalized pillared-layered metal–organic frameworks

Abstract

Co-adsorption measurements reveal the flexible and gas separation behavior of functionalized pillared-layered MOFs when exposed to gas mixtures.

Pillared-layered metal–organic frameworks for mechanical energy storage applications

“…37 While theoretical investigations of DMOF-1 are relatively limited, 5,17,21,38,39 the unusual and reversible breathing behavior has been highlighted by several experimental groups. 29,[40][41][42][43][44][45][46][47][48][49][50][51][52][53][54] On the one hand, with guests present in the pores, DMOF-1(Zn) was found to contract upon adsorption. Specic guest molecules such as benzene, methanol, ethanol and isopropanol (IPA) trigger breathing, 29,40,42,50 while N,N-dimethylformamide (DMF) distorts the structure in a different way.…”

“…Functionalization also allowed to inuence the guest-dependent behavior. [41][42][43][44]47,49,51,52 Very recently, Fischer and co-workers discussed into detail the signicant impact of the metal ion on the breathing mechanisms in a functionalized DMOF-1. 53 Previous studies highlighted how the threshold gas pressure and transition temperature for the breathing transition can be tuned by the choice of the functional groups and metal ion.…”

Assembly of a series of zinc coordination polymers based on 5-functionalized isophthalic acids and dipyridyl

“…[23][24][25] In recent years, functionalized polycarboxylic acid derivatives have been extensively used as multifunctional organic ligands in the formation of coordination frameworks owing to their high stability, various coordination modes and strong coordination ability toward transition metal ions. [26][27][28][29][30] Among them, 5-functionalized isophthalates are good candidates within coordination and supramolecular chemistry because their two V-shaped carboxylate groups may bridge metal ions or metal clusters via versatile coordination modes similar to that of isophthalate. [31][32][33][34][35][36][37][38][39][40] For example, McCormick et al found that the topology of CPs is dependent on the combination of solvent system used and length of the functionalized-groups.…”

Tetracarboxylate Linker-Based Flexible CuII Frameworks: Efficient Separation of CO2 from CO2/N2 and C2H2 from C2H2/C2H4 Mixtures

“…30,31 Furthermore, the flexibility of such ligands contributes to the tunable porosity of MOFs by inducing guest-responsive structural dynamicity 23,31,32,50 with the ability to respond to external stimuli, 33 for example, temperature, pressure, light, electric fields, and chemical inclusion. 11,32 Such dynamic frameworks 34 also manifest stepwise 35 or gated adsorption 36,37 at a certain pressure of an adsorbate molecule 38,39 which results in guest selectivity 31,40 and gas separation. 40−42…”

“…Multidentate flexible linkers, for example, di, tri, and tetra carboxylates, − , are the most widely used linkers in MOF chemistry. , Such linkers coordinate with metal ions to form a wide range of multinuclear nodes with predictable geometries such as binuclear paddle-wheel units, tri, or tetranuclear units . In this regard, aromatic tetracarboxylate linkers are particularly utilitarian because of the more number of coordinating sites as well as the rich π-electron density. , MOFs constructed from such π-electron-rich tetracarboxylate ligands have pore surfaces studded with a large number of oxygen atoms providing better interactions with gas molecules such as CO 2 , or small hydrocarbon molecules such as ethylene and acetylene. , Furthermore, the flexibility of such ligands contributes to the tunable porosity of MOFs by inducing guest-responsive structural dynamicity ,,, with the ability to respond to external stimuli, for example, temperature, pressure, light, electric fields, and chemical inclusion. , Such dynamic frameworks also manifest stepwise or gated adsorption , at a certain pressure of an adsorbate molecule , which results in guest selectivity , and gas separation. − …”