Gas Sorption Properties of Isostructural Co-MOFs Containing Dipyridylporphyrin Linkers with Different Substituents at the 10,20-meso-Positions

In Hwan Choi, Seung Hyun Chae, Seong Huh, Suk Joong Lee, Sung Jin Kim, Youngmee Kim

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Two new isostructural 3D dipyridylporphyrin-based MOFs, [Co(DpyDClP)]6·18H2O (I) and [Co(DpyDCNP)]6·18H2O (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 N2, H2, and CH4 by the two MOFs was also investigated.

Original languageEnglish
Pages (from-to)2989-2995
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Volume2015
Issue number18
DOIs
Publication statusPublished - 2015 Jun 1

Keywords

  • Carbon dioxide
  • Cobalt
  • Gas sorption
  • Metal-organic frameworks
  • Porphyrins

ASJC Scopus subject areas

  • Inorganic Chemistry

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