Structure and Redox Tuning of Gas Adsorption Properties in Calixarene-supported Fe(ii)-based Porous Cages

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Jun 14

PMID 34122984

Citations 4

Authors

Meaghan M Deegan

Tonia S Ahmed

Glenn P A Yap

Eric D Bloch

Affiliations

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Abstract

We describe the synthesis of Fe(ii)-based octahedral coordination cages supported by calixarene capping ligands. The most porous of these molecular cages has an argon accessible BET surface area of 898 m g (1497 m g Langmuir). The modular synthesis of molecular cages allows for straightforward substitution of both the bridging carboxylic acid ligands and the calixarene caps to tune material properties. In this context, the adsorption enthalpies of C/C hydrocarbons ranged from -24 to -46 kJ mol at low coverage, where facile structural modifications substantially influence hydrocarbon uptakes. These materials exhibit remarkable stability toward oxidation or decomposition in the presence of air and moisture, but application of a suitable chemical oxidant generates oxidized cages over a controlled range of redox states. This provides an additional handle for tuning the porosity and stability of the Fe cages.

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References

Liu M, Liao W, Hu C, Du S, Zhang H . Calixarene-based nanoscale coordination cages. Angew Chem Int Ed Engl. 2012; 51(7):1585-8. DOI: 10.1002/anie.201106732. View

Lorzing G, Gosselin A, Trump B, York A, Sturluson A, Rowland C . Understanding Gas Storage in Cuboctahedral Porous Coordination Cages. J Am Chem Soc. 2019; 141(30):12128-12138. PMC: 6746114. DOI: 10.1021/jacs.9b05872. View

Park J, Perry Z, Chen Y, Bae J, Zhou H . Chromium(II) Metal-Organic Polyhedra as Highly Porous Materials. ACS Appl Mater Interfaces. 2017; 9(33):28064-28068. DOI: 10.1021/acsami.7b09339. View

Dai F, Sambasivam U, Hammerstrom A, Wang Z . Synthetic supercontainers exhibit distinct solution versus solid state guest-binding behavior. J Am Chem Soc. 2014; 136(20):7480-91. DOI: 10.1021/ja502839b. View

Li J, Yakovenko A, Lu W, Timmons D, Zhuang W, Yuan D . Ligand bridging-angle-driven assembly of molecular architectures based on quadruply bonded Mo-Mo dimers. J Am Chem Soc. 2010; 132(49):17599-610. DOI: 10.1021/ja1080794. View

Reed D, Xiao D, Jiang H, Chakarawet K, Oktawiec J, Long J . Biomimetic O adsorption in an iron metal-organic framework for air separation. Chem Sci. 2021; 11(6):1698-1702. PMC: 8148054. DOI: 10.1039/c9sc06047b. View

Bloch E, Queen W, Hudson M, Mason J, Xiao D, Murray L . Hydrogen Storage and Selective, Reversible O2 Adsorption in a Metal-Organic Framework with Open Chromium(II) Sites. Angew Chem Int Ed Engl. 2016; 55(30):8605-9. DOI: 10.1002/anie.201602950. View

Furukawa H, Cordova K, OKeeffe M, Yaghi O . The chemistry and applications of metal-organic frameworks. Science. 2013; 341(6149):1230444. DOI: 10.1126/science.1230444. View

Tan H, Du S, Bi Y, Liao W . Two 2D metal-calixarene aggregates incorporating pre-designed coordination nanocages. Chem Commun (Camb). 2013; 49(74):8211-3. DOI: 10.1039/c3cc42259c. View

10.

Chui , LO , Charmant , Orpen , Williams . A chemically functionalizable nanoporous material. Science. 1999; 283(5405):1148-50. DOI: 10.1126/science.283.5405.1148. View

11.

Murray L, Dinca M, Yano J, Chavan S, Bordiga S, Brown C . Highly-selective and reversible O2 binding in Cr3(1,3,5-benzenetricarboxylate)2. J Am Chem Soc. 2010; 132(23):7856-7. DOI: 10.1021/ja1027925. View

12.

Eddaoudi M, Kim J, Wachter J, Chae H, OKeeffe M, Yaghi O . Porous metal-organic polyhedra: 25 A cuboctahedron constructed from 12 Cu2(CO2)4 paddle-wheel building blocks. J Am Chem Soc. 2001; 123(18):4368-9. DOI: 10.1021/ja0104352. View

13.

Ma S, Zhou H . A metal-organic framework with entatic metal centers exhibiting high gas adsorption affinity. J Am Chem Soc. 2006; 128(36):11734-5. DOI: 10.1021/ja063538z. View

14.

Netzer N, Dai F, Wang Z, Jiang C . pH-modulated molecular assemblies and surface properties of metal-organic supercontainers at the air-water interface. Angew Chem Int Ed Engl. 2014; 53(41):10965-9. DOI: 10.1002/anie.201406733. View

15.

Dai F, Becht D, Wang Z . Modulating guest binding in sulfonylcalixarene-based metal-organic supercontainers. Chem Commun (Camb). 2013; 50(40):5385-7. DOI: 10.1039/c3cc47420h. View

16.

Yuan S, Huang L, Huang Z, Sun D, Qin J, Feng L . Continuous Variation of Lattice Dimensions and Pore Sizes in Metal-Organic Frameworks. J Am Chem Soc. 2020; 142(10):4732-4738. DOI: 10.1021/jacs.9b13072. View

17.

Bloch E, Murray L, Queen W, Chavan S, Maximoff S, Bigi J . Selective binding of O2 over N2 in a redox-active metal-organic framework with open iron(II) coordination sites. J Am Chem Soc. 2011; 133(37):14814-22. DOI: 10.1021/ja205976v. View

18.

Eddaoudi M, Kim J, Rosi N, Vodak D, Wachter J, OKeeffe M . Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science. 2002; 295(5554):469-72. DOI: 10.1126/science.1067208. View

19.

Anderson J, Gallagher A, Mason J, Harris T . A five-coordinate heme dioxygen adduct isolated within a metal-organic framework. J Am Chem Soc. 2014; 136(47):16489-92. DOI: 10.1021/ja5103103. View

20.

Gosselin A, Lorzing G, Trump B, Brown C, Bloch E . Gas adsorption in an isostructural series of pillared coordination cages. Chem Commun (Camb). 2018; 54(49):6392-6395. DOI: 10.1039/c8cc03216e. View