Trends in Chemistry
ReviewCatalytic Porphyrin Framework Compounds
Section snippets
Porphyrin Framework Compounds
Porphyrins are a series of substituted porphine compounds that contain heterocyclic macrocycles [1., 2., 3.]. The name porphyrin originates from the purple coloration that results from light adsorption of the large porphyrin conjugated system in the visible region of the light spectrum. Porphyrin-related compounds are commonly observed in nature and function as essential catalysts for various processes [4,5]. For example, a porphyrin derivative, heme, can act as a cofactor of hemoglobin in red
Synthesis and Structural Description of Porphyrin MOFs
MOFs, a well-established class of framework compounds, contain nanoscale pores that can be utilized for recognition, storage, and conversion [14., 15., 16., 17.]. The modular nature of MOFs permits researchers to design topologies, adjust porosities, and tune functionalities within a single framework by selecting suitable inorganic and organic building blocks [18,19]. These framework compounds are an excellent platform for aligning and assigning porphyrin functional groups at specific distances
Synthesis and Structural Description of Porphyrin COFs
COFs are a class of emerging porous materials with high chemical and thermal stability, in which organic building units are bridged through covalent bonds [62]. The periodic framework and ordered arrangement of pore spaces in COFs allow for precise structural characterization using techniques such as electron diffraction, single-crystal, or powder X-ray diffraction [63]. Similar to MOF chemistry, the topology and porosity of COFs can also be predesigned by controlling monomer geometry and
Lewis Acid Catalysis
Porphyrins with unsaturated metal centers within framework compounds can function as efficient Lewis acid catalysts by offering available coordination sites and facilitating the catalytic transformation within open pore spaces of framework compounds (Table 2). One model reaction is the ring-opening of styrene epoxide with trimethylsilylazide (TMSN3). Takaishi, Farha, Hupp, and coworkers reported a Zn-based porphyrin MOF (ZnAl-RPM) that could catalyze this ring-opening reaction efficiently due
Concluding Remarks
In summary, we discuss the structures and recent catalytic applications of porphyrin framework compounds that have been studied over the last decade. Extensive efforts have been made to design porphyrinic building blocks with various sizes, geometries, connectivity, substituents, and functional groups, which are then used as linkers in MOFs and monomers in COFs. The efficient synthetic strategies, guided by reticular chemistry for the construction of porphyrin framework compounds, were
Acknowledgments
We would like to thank the Center for Gas Separations, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award Number DE-SC0001015 and the Robert A. Welch Foundation through a Welch Endowed Chair to H-C.Z. (A-0030).
Disclaimer Statement
The authors declare no competing interest.
Glossary
- Building block
- organic linkers or metal clusters serving as joints in framework compounds.
- Covalent organic framework (COF)
- porous, crystalline 2D or 3D polymers connected by covalent bonds.
- Interpenetration
- intergrowth of a secondary framework within the voids of a parent framework.
- Isostructure
- two framework compounds with the same topology, derived from similar connectivity and geometry of building units.
- Metal–organic framework (MOF)
- a porous and crystalline coordination polymer comprised of organic
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These authors contributed equally to this work
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