Gas Sorption Properties of Isostructural Co-MOFs Containing Dipyridylporphyrin Linkers with Different Substituents at the 10,20-meso-Positions
- Authors
- Choi, In-Hwan; Chae, Seung Hyun; Huh, Seong; Lee, Suk Joong; Kim, Sung-Jin; Kim, Youngmee
- Issue Date
- 6월-2015
- Publisher
- WILEY-V C H VERLAG GMBH
- Keywords
- Porphyrins; Cobalt; Gas sorption; Carbon dioxide; Metal-organic frameworks
- Citation
- EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, no.18, pp.2989 - 2995
- Indexed
- SCIE
SCOPUS
- Journal Title
- EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
- Number
- 18
- Start Page
- 2989
- End Page
- 2995
- URI
- https://scholar.korea.ac.kr/handle/2021.sw.korea/132752
- DOI
- 10.1002/ejic.201500294
- ISSN
- 1434-1948
- Abstract
- Two new isostructural 3D dipyridylporphyrin-based MOFs, [Co(DpyDClP)](6)18H(2)O (I) and [Co(DpyDCNP)](6)18H(2)O (II), were prepared and structurally characterized by X-ray crystallography [DpyDClP: 5,15-di(4-pyridyl)-10,20-di(4-chlorophenyl)porphyrin; DpyDCNP: 5,15-di(4-pyridyl)-10,20-di(4-cyanophenyl)porphyrin]. They display exactly the same framework structures, notwithstanding different substituents at the 10,20-meso-positions of the dipyridylporphyrin backbones. Both substituents, -Cl for I and -CN for II, are completely exposed to the open space of solvent-free I and II. Therefore, the two MOFs have the same framework structures with distinct pore functionalities. Solvent-free I and II have solvent-accessible void volumes of 17.3 and 14.9%, respectively. The thermal properties of I and II are very similar, but the gas sorption properties strongly depend on the pore dimensions and functionalities. Compound I has a higher uptake of CO2 compared with that of II due to its larger void volume. Particularly, CO2 sorption isotherms at 196 K indicate dramatically different patterns depending on the meso-substituents. Whereas I shows S-shape isotherms for CO2 adsorption/desorption at 196 K, II does not. The sorption of N-2, H-2, and CH4 by the two MOFs was also investigated.
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