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.

Coordination polymers have been emerging as a topical research field in crystal engineering, solid-state chemistry, and materials science. Considering the wide occurrence of structural and compositional diversity during self-assembly and crystallization, supramolecular isomerism represents an indication of composition control and structure prediction. Actually, supramolecular isomerism is not just an obstacle or challenge, but also a good opportunity for developing novel materials and a better understanding of self-assembly and crystal growth. This critical review provides an overview of the developing knowledge, in the context of supramolecular isomerism, of the design, synthesis, and properties of coordination polymers (97 references).

One-pot solvothermal treatments of organonitriles, ammonia, and Cu(II) salts yielded Cu(I) and 3,5-disubstituted 1,2,4-triazolates. The organic triazolate components were derived from copper-mediated oxidative cycloaddition of nitriles and ammonia, in which a key intermediate 1,3,5-triazapentadienate was isolated as [Cu(II)(4-pytap)(2)] (4-Hpytap = 2,4-di(4-pyridyl)-1,3,5-triazapentadiene) via controlled solvothermal conditions. This intermediate could also be synthesized by Ni(II)-mediated reactions; however, the final triazoles were obtained only when Cu(II) was employed. Therefore, the reaction mechanism of these reactions was elucidated as follows: nitrile was first attacked by ammonia to form the amidine, which further reacted with another nitrile or self-condensed to yield 1,3,5-triazapentadiene, which was coordinated to two Cu(II) ions in its deprotonated form. A two-electron oxidation of the 1,3,5-triazapentadienate mediated by two Cu(II) ions gave one triazolate and Cu(I) cations. Other in situ ligand reactions, such as C-C bond cleavage and hydrolysis, were also found for the nitriles under these solvothermal conditions. Another remarkable feature of these crystalline Cu(I) triazolates is their simple, typical 3- or 4-connected network topologies. The self-assembly of these nets is presumably controlled by steric hindrance, which is subsequently applied to the rational design of the close-packed 2D networks [Cu(I)(tz)](infinity) and [Ag(I)(tz)](infinity) (Htz = 1,2,4-triazole), as well as the porous 3D network [Cu(I)(etz)](infinity) (Hetz = 3,5-diethyl-1,2,4-triazole). The interesting photoluminescence properties of these coinage d(10) metal complexes were also investigated.

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.