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Title: Structure and redox tuning of gas adsorption properties in calixarene-supported Fe( ii )-based porous cages

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 m2 g-1 (1497 m2 g-1 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 C2/C3 hydrocarbons ranged from -24 to -46 kJ mol-1 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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry & Biochemistry, University of Delaware, Newark, USA
  2. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, USA
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
OSTI Identifier:
1618159
Alternate Identifier(s):
OSTI ID: 1799550
Grant/Contract Number:  
EE0008813
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 20; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Deegan, Meaghan M., Ahmed, Tonia S., Yap, Glenn P. A., and Bloch, Eric D. Structure and redox tuning of gas adsorption properties in calixarene-supported Fe( ii )-based porous cages. United Kingdom: N. p., 2020. Web. doi:10.1039/D0SC01833C.
Deegan, Meaghan M., Ahmed, Tonia S., Yap, Glenn P. A., & Bloch, Eric D. Structure and redox tuning of gas adsorption properties in calixarene-supported Fe( ii )-based porous cages. United Kingdom. https://doi.org/10.1039/D0SC01833C
Deegan, Meaghan M., Ahmed, Tonia S., Yap, Glenn P. A., and Bloch, Eric D. 2020. "Structure and redox tuning of gas adsorption properties in calixarene-supported Fe( ii )-based porous cages". United Kingdom. https://doi.org/10.1039/D0SC01833C.
@article{osti_1618159,
title = {Structure and redox tuning of gas adsorption properties in calixarene-supported Fe( ii )-based porous cages},
author = {Deegan, Meaghan M. and Ahmed, Tonia S. and Yap, Glenn P. A. and Bloch, Eric D.},
abstractNote = {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 m2 g-1 (1497 m2 g-1 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 C2/C3 hydrocarbons ranged from -24 to -46 kJ mol-1 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.},
doi = {10.1039/D0SC01833C},
url = {https://www.osti.gov/biblio/1618159}, journal = {Chemical Science},
issn = {2041-6520},
number = 20,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1039/D0SC01833C

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