synthesis-characterization-functionalized-metal-organic

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Northwestern University

A zeolitic imidazolate framework material of SOD topology possessing primarily unsubstituted imidazolate (im) linkers has been synthesized via solvent-assisted linker exchange (SALE) of ZIF-8. The structure of the new material, SALEM-2, has been confirmed through (1)H NMR and powder and single-crystal X-ray diffraction. SALEM-2 is the first example of a porous Zn(im)(2) ZIF possessing a truly zeolitic topology that can be obtained in bulk quantities. Upon treatment with n-butyllithium, the open analogue exhibits BrÃ¸nsted base catalysis that cannot be accomplished by the parent material ZIF-8. Additionally, it displays a different size cutoff for uptake and release of molecular guests than does ZIF-8.

Opening ZIF-8: a catalytically active zeolitic imidazolate framework of sodalite topology with unsubstituted linkers.

The aromatizing ring-closing metathesis has been shown to take place inside an extended porous framework. Employing a combination of solvent-assisted linker exchange and postsynthesis modification using olefin metathesis, the noninterpenetrated SALEM-14 was formed and converted catalytically into PAH-MOF-1 with polycyclic aromatic hydrocarbon (PAH) pillars. The metal-organic framework in SALEM-14 prevents "intermolecular" olefin metathesis from occurring between the pillars in the presence of the first generation Hoveyda-Grubbs catalyst, while favoring the production of a PAH, which can be released from the framework under acidic conditions in dimethylsulfoxide.

Aromatizing olefin metathesis by ligand isolation inside a metal-organic framework.

Metal-organic frameworks (MOFs) have gained considerable attention as hybrid materials-in part because of a multitude of potential useful applications, ranging from gas separation to catalysis and light harvesting. Unfortunately, de novo synthesis of MOFs with desirable function-property combinations is not always reliable and may suffer from vagaries such as formation of undesirable topologies, low solubility of precursors, and loss of functionality of the sensitive network components. The recently discovered synthetic approach coined solvent-assisted linker exchange (SALE) constitutes a simple to implement strategy for circumventing these setbacks; its use has already led to the generation of a variety of MOF materials previously unobtainable by direct synthesis methods. This Review provides a perspective of the achievements in MOF research that have been made possible with SALE and examines the studies that have facilitated the understanding and broadened the scope of use of this invaluable synthetic tool.

Solvent-assisted linker exchange: an alternative to the de novo synthesis of unattainable metal-organic frameworks.

Metal-organic frameworks (MOFs) are hybrid porous materials with many potential applications, which intimately depend on the presence of chemical functionality either at the organic linkers and/or at the metal nodes. Functionality that cannot be introduced into MOFs directly via de novo syntheses can be accessed through post-synthesis modification (PSM) on the reactive moieties of the linkers and/or nodes without disrupting the metal-linker bonds. Even more intriguing methods that go beyond PSM are herein termed building block replacement (BBR) which encompasses (i) solvent-assisted linker exchange (SALE), (ii) non-bridging ligand replacement, and (iii) transmetalation. These one-step or tandem BBR processes involve exchanging key structural components of the MOF, which in turn should allow for the evolution of protoMOF structures (i.e., the utilization of a parent MOF as a template) to design MOFs composed of completely new components, presumably via single crystal to single crystal transformations. The influence of building block replacement on the stability and properties of MOFs will be discussed, and some insights into their mechanistic aspects are provided. Future perspectives providing a glimpse into how these techniques can lead to various unexplored areas of MOF chemistry are also presented.

Article	Year
Opening ZIF-8: a catalytically active zeolitic imidazolate framework of sodalite topology with unsubstituted linkers. Journal of the American Chemical Society\| PubMed ID: 23088345	2012
Aromatizing olefin metathesis by ligand isolation inside a metal-organic framework. Journal of the American Chemical Society\| PubMed ID: 24047342	2013
Solvent-assisted linker exchange: an alternative to the de novo synthesis of unattainable metal-organic frameworks. Angewandte Chemie (International ed. in English)\| PubMed ID: 24652755	2014
Beyond post-synthesis modification: evolution of metal-organic frameworks via building block replacement. Chemical Society reviews\| PubMed ID: 24723093	2014

Olga Karagiaridi

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