Trends in Chemistry
Volume 2, Issue 6, June 2020, Pages 555-568
Journal home page for Trends in Chemistry

Review
Catalytic Porphyrin Framework Compounds

https://doi.org/10.1016/j.trechm.2020.01.003Get rights and content

Highlights

  • Precise immobilization of porphyrin building blocks into crystalline framework materials, including metal–organic frameworks and covalent organic frameworks, has been achieved and summarized.

  • By rational design of porphyrin building blocks with varying sizes, tunable geometry, connectivity, and diverse substitutes, functional porphyrin framework compounds with targeted topologies can be fabricated.

  • The multifunctional properties of porphyrin units within the frameworks allow for a variety of catalytic reactions within pore spaces, including Lewis acid catalysis, oxidation catalysis, photocatalysis, and electrocatalysis.

  • The tunability of the porphyrin substitutes or surrounding functional groups within the framework provides an effective approach for the optimization of catalytic activity and selectivity.

Porphyrins are frequently observed in nature and play a vital role in many biological functions, including light-harvesting, oxygen transport, and catalytic transformations. The rigid, robust, and multifunctional features of porphyrins enable the construction of framework compounds such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) for use in several important applications. This short review summarizes the types of porphyrin building blocks with varying connectivity, their assembly into framework compounds, and key structural factors governing porphyrin ligand design. Furthermore, we highlight emerging catalytic applications of these porphyrin framework compounds as Lewis acid catalysts, oxidation catalysts, photocatalysts, and electrocatalysts. Together, this review supplies a timely update on porphyrin ligand design and framework compound synthesis and guides the future development of porphyrin framework compounds with diverse functionalities for efficient catalysis.

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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