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Conceptual Advances from Werner Complexes to Metal-Organic Frameworks.

ABSTRACT: Alfred Werner's work on the geometric aspects of how ligands bind to metal ions at the end of the 19th century has given rise, in the molecular realm, to organometallic, bioinorganic, and cluster chemistries. By stitching together organic and inorganic units into crystalline porous metal-organic frameworks (MOFs), the connectivity, spatial arrangement, and geometry of those molecular complexes can now be fixed in space and become directly addressable. The fact that MOFs are porous provides additional space within which molecules can further be transformed and their chemistry controlled. An aspect not available in molecular chemistry but a direct consequence of Werner's analysis of coordination complexes is the ability to have multivariable functionality in MOFs to bring about a continuum of chemical environments, within the repeating order of the framework, from which a substrate can sample and be transformed in ways not possible in molecular complex chemistry.

SUBMITTER: Diercks CS

PROVIDER: S-EPMC6276034 | biostudies-other | 2018 Nov

REPOSITORIES: biostudies-other

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Conceptual Advances from Werner Complexes to Metal-Organic Frameworks.

Diercks Christian S CS Kalmutzki Markus J MJ Diercks Nicolas J NJ Yaghi Omar M OM

ACS central science 20181022 11

Alfred Werner's work on the geometric aspects of how ligands bind to metal ions at the end of the 19th century has given rise, in the molecular realm, to organometallic, bioinorganic, and cluster chemistries. By stitching together organic and inorganic units into crystalline porous metal-organic frameworks (MOFs), the connectivity, spatial arrangement, and geometry of those molecular complexes can now be fixed in space and become directly addressable. The fact that MOFs are porous provides addit ...[more]

PMID: 30555897

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Project description:Metal-organic frameworks are a class of porous crystalline materials based on the ordered connection of metal centers or metal clusters by organic linkers with comprehensive functionalities. The interest in these materials is rapidly moving towards their application in industry and real life. In this context, cheap and sustainable synthetic strategies of MOFs with tailored structures and functions are nowadays a topic widely studied from different points of view. In this review, fluorinated MOFs (F-MOFs) and their applications are investigated. The principal aim is to provide an overview of the structural features and the main application of MOFs containing fluorine atoms both as anionic units or as coordinating elements of more complex inorganic units and, therefore, directly linked to the structural metals or as part of fluorinated linkers used in the synthesis of MOFs. Herein we present a review of F-MOFs reported in the recent literature compared to benchmark compounds published over the last 10 years. The compounds are discussed in terms of their structure and properties according to the aforementioned classification, with an insight into the different chemical nature of the bonds. The application fields of F-MOFs, especially in sustainability related issues, such as harmful gas sorption and separation, will also be discussed. F-MOFs are compounds containing fluorine atoms in their framework and they can be based on: (a) fluorinated metallic or semi-metallic anionic clusters or: (b) fluorinated organic linkers or (c) eventually containing both the building blocks. The nature of a covalent C-F bond in terms of length, charge separation and dipole moment sensibly differs from that of a partly ionic M-F (M = metal) one so that the two classes of materials (points a and b) have different properties and they find various application fields. The study shows how the insertion of polar M-F and C-F bonds in the MOF structure may confer several advantages in terms of interaction with gaseous molecules and the compounds can find application in gas sorption and separation. In addition, hydrophobicity tends to increase compared to non-fluorinated analogues, resulting in an overall improvement in moisture stability.

Dataset Information

Conceptual Advances from Werner Complexes to Metal-Organic Frameworks.

Publications

Conceptual Advances from Werner Complexes to Metal-Organic Frameworks.

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