Metal Azolate Frameworks: From Crystal Engineering to Functional Materials

Self-catalysed aerobic oxidization of organic linker in porous crystal for on-demand regulation of sorption behaviours

“…Table 1) showed that MAF-42-lp is a threedimensional (3D) porous coordination framework composed of five independent (two of them locate at twofold axes with occupancies of 1/2) Cu(I) ions and two independent, fully deprotonated btm 2 À ligands in a 2:1 molar ratio. As expected, all btm 2 À ligands are six-coordinated and the average coordination number of Cu(I) ions is three 4 . Nevertheless, each Cu(I) ion either adopts the linear, distorted T-shaped or tetrahedral coordination geometry ( Supplementary Fig.…”

“…Although Cu(I)-based PCPs are very scarce because Cu(I) can be easily oxidized as Cu(II) by air to destroy the original metal-ligand connectivity 31 , azolate derivatives have been demonstrated as suitable ligands for highly stable PCPs even with Cu(I) (ref. 4), and the coordination between Cu(I) and triazolate can be expected to give low-coordinated metal centres similar to those in the O 2 -activating copper proteins. Furthermore, the methylene bridge in a diarylmethane-type ligand is obviously flexible and oxidizable (activated by two aromatic rings) 32 , which could be oxidized in suitable catalytic conditions to form a more rigid and polar ketone group.…”

“…C ompared with conventional adsorbents, porous coordination polymers (PCPs) are unique for their diversified and tailorable coordination frameworks [1][2][3][4][5][6][7][8][9][10][11] . While tailoring structure/property generally refers to design/synthesis of new ligands and frameworks, some PCP prototypes can adopt several different metal ions and/or ligands, providing a rational strategy for adjusting the structure/property, albeit only in a limited degree 5,8,[12][13][14] .…”

“…Considering that PCPs generally lack sufficient robustness, reactivity and/or O 2 -activation ability to allow aerobic oxidation of themselves, we designed and synthesized a porous metal azolate framework (MAF) 4 on the basis of Cu(I) and a methylene-bridged bis-triazolate ligand (Fig. 1).…”

The First Example of Hetero‐Triple‐Walled Metal–Organic Frameworks with High Chemical Stability Constructed via Flexible Integration of Mixed Molecular Building Blocks

“…Metal‐organic frameworks (MOFs) are highly impressive for their remarkable diversity in terms of compositions and structures,1, 2, 3, 4, 5 which has been regarded as a driving source of their great potential in various applications, including gas storage, separation, catalysis, sensing, and recognition, and drug delivery, among others 6, 7, 8, 9, 10. Thus, novel and unique crystalline MOF structures have been vigorously pursued in the past decade, leading to widespread efforts by increasing the level of structural complexity to attain more fascinating architectures, such as cage‐in‐cage,11, 12 polyhedron,13, 14 high nuclearity,15, 16 and etc 17, 18.…”