Metal–organic frameworks (MOFs) allow compositional and structural diversity beyond conventional solid-state materials. Continued interest in the field is justified by potential applications of exceptional breadth, ranging from gas storage and separation, which takes advantage of the inherent pores and their volume, to electronic applications, which requires precise control of electronic structure. In this Outlook we present some of the pertinent challenges that MOFs face in their conventional implementations, as well as opportunities in less traditional areas. Here the aim is to discuss select design concepts and future research goals that emphasize nuances relevant to this class of materials as a whole. Particular emphasis is placed on synthetic aspects, as they influence the potential for MOFs in gas separation, electrical conductivity, and catalytic applications.

Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable nonvolatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal−organic framework (MOF) to produce stable and safe-tohandle Co(III) materials featuring terminal Co(III)−halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)−halogen bonds, reduction to Co(II), and concomitant release of elemental halogens. The reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, as the parent cobaltous MOF retains its crystallinity and porosity even after three oxidation/reduction cycles. These results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.

Vanadium catalysts offer unique selectivity in olefin polymerization, yet are underutilized industrially owing to their poor stability and productivity. Reported here is the immobilization of vanadium by cation exchange in MFU-4l, thus providing a metal-organic framework (MOF) with vanadium in a molecule-like coordination environment. This material forms a single-site heterogeneous catalyst with methylaluminoxane and provides polyethylene with low polydispersity (PDI≈3) and the highest activity (up to 148 000 h ) reported for a MOF-based polymerization catalyst. Furthermore, polyethylene is obtained as a free-flowing powder as desired industrially. Finally, the catalyst shows good structural integrity and retains polymerization activity for over 24 hours, both promising attributes for the commercialization of vanadium-based polyolefins.

The zirconium nodes of the metal-organic framework (MOF) known as NU-1000 serve as competent supports for the activation of methyltrioxorhenium (MTO) toward olefin metathesis. Itself inactive for olefin metathesis, MTO becomes an active catalyst only when immobilized on the strongly acidic Lewis acid sites of dehydrated NU-1000. Uptake of MTO at the dehydrated secondary building units (SBUs) occurs rapidly and quantitatively to produce a catalyst active in both gas- and liquid-phase processes. These results demonstrate for the first time the utility of MOF SBUs for olefin metathesis, an academically and industrially relevant transformation.

Reactions between O 2 and organometallics with non-redox-active metal centers have received continuous interest foro ver1 50 years, althoughs ignificant uncertainties concerningt he character and details of the actual mechanism of these reactions persist. Harnessingd inuclear threecoordinate alkylzinc derivatives of an N,N-coupled bis(b-diketimine) proligand (LH 2 )a sam odel system, we demonstrate for the first time that as light modification of the reaction conditions might have ad ramatic influence on the oxygenation reaction outcomes, leading to an unprecedented variety of products originating from as ingle reaction system,t hat is, partially and fully oxygenated zinc alkoxides,zinc alkylperoxides, and zinc hydroxide compounds. Our studies indicate that accessibility of the three-coordinate zinc center by the O 2 molecule, coupled with the lower reactivity of Zn-Me vs.