Thermally robust porous metal–organic frameworks (MOFs) with zeolitic topologies were constructed by means of a ligand‐directed strategy involving molecular tailoring of simple bridging imidazolates with coordinatively unimportant substituents. This led to the isolation of three new MOFs having unusually high symmetries, intriguing topologies such as the supercage shown in the picture, and high thermal stability.

Conventional adsorbents preferentially adsorb the small, high-polarity, and unsaturated 1,3-butadiene molecule over the other C hydrocarbons from which it must be separated. We show from single-crystal x-ray diffraction and computational simulation that a hydrophilic metal-organic framework, [Zn(btm)], where Hbtm is bis(5-methyl-1-1,2,4-triazol-3-yl)methane, has quasi-discrete pores that can induce conformational changes in the flexible guest molecules, weakening 1,3-butadiene adsorption through a large bending energy penalty. In a breakthrough operation at ambient temperature and pressure, this guest conformation-controlling adsorbent eluted 1,3-butadiene first, then butane, butene, and isobutene. Thus, 1,3-butadiene can be efficiently purified (≥99.5%) while avoiding high-temperature conditions that can lead to its undesirable polymerization.

Porous materials capable of selectively capturing CO 2 from flue-gases or natural gas are of interest in terms of rising atmospheric CO 2 levels and methane purification. Sizeexclusive sieving of CO 2 over CH 4 and N 2 has rarely been achieved. Herein we show that acrystal engineering approach to tuning of pore-size in ac oordination network, [Cu(quinoline-5-carboxyate) 2 ] n (Qc-5-Cu)ena+bles ultra-high selectivity for CO 2 over N 2 (S CN % 40 000) and CH 4 (S CM % 3300). Qc-5-Cu-sql-b,anarrowpore polymorph of the square lattice (sql) coordination network Qc-5-Cu-sql-a, adsorbs CO 2 while excluding both CH 4 and N 2 .E xperimental measurements and molecular modeling validate and explain the performance. Qc-5-Cu-sql-b is stable to moisture and its separation performance is unaffected by humidity.

Gas sorption experiments and grand canonical Monte Carlo simulations for two isostructural microporous metal azolate frameworks show that even partially exposed uncoordinated nitrogens can effectively increase gas binding affinity and overcome the pore size confinement effect.

Thermisch robuste poröse metall‐organische Gerüste (MOFs) mit Zeolithstruktur wurden mithilfe einer ligandgesteuerten Strategie aufgebaut, die auf der Modifizierung einfacher Imidazolate als Brückenspezies durch nichtkoordinierende Substituenten beruht. Drei neue MOFs mit ungewöhnlichen Topologien (siehe Bild) und hoher thermischer Stabilität wurden isoliert.