CO2 selective 1D double chain dipyridyl-porphyrin based porous coordination polymers

Hyun Chul Kim, Young Sun Lee, Seong Huh, Suk Joong Lee, Youngmee Kim

Research output: Contribution to journalArticle

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Abstract

Thermal reactions of MnCl(DPyP) (DPyP = 5,15-di(4-pyridyl)-10,20- diphenylporphyrin) as a metalloligand with CoII and ZnII ions in dimethylformamide led to neutral one-dimensional (1D) double chain dipyridyl-porphyrin-based porous coordination polymers (PCPs), Co 3(DPyP)3·4DMF (I) and Zn3(DPyP) 3·2DMF·4H2O (II). Both PCPs were structurally characterized by X-ray crystallography. Particularly, the central MnIII ion in MnCl(DPyP) was transmetallated with CoII or ZnII ions and the central CoII or ZnII ions were further coordinated to pyridyl groups of neighboring M(DPyP) (M = Co or Zn) porphyrin complexes. PCPs I and II are isostructural and each 1D double chain interacts with another 1D double chain by multiple hydrogen bonding to stabilize the resulting framework. Therefore, solvent-free 1D double chain PCPs have permanent porosity, and the void volumes of the solvent-free I and II are calculated to be 22.6% and 23.0%, respectively. Gas sorption analysis indicated that I and II exhibited selective adsorption of CO2 at 196 K. Both PCPs exhibited much smaller sorption abilities for N2 (77 K), H 2 (77 K), and CH4 (196 K) than CO2 (196 K). Both PCPs exhibited different PXRD patterns when dried at 373 K, which indicated that the framework transformation of the isostructural M3(DPyP) 3 type of PCPs strongly depended on the type of central metal ions.

Original languageEnglish
Pages (from-to)5680-5686
Number of pages7
JournalDalton Transactions
Volume43
Issue number15
DOIs
Publication statusPublished - 2014 Apr 21

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Porphyrins
Polymers
Ions
Sorption
Dimethylformamide
Porosity
X ray crystallography
X Ray Crystallography
Hydrogen Bonding
Adsorption
Metal ions
Hydrogen bonds
Hot Temperature
Gases
Metals

ASJC Scopus subject areas

  • Inorganic Chemistry

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CO2 selective 1D double chain dipyridyl-porphyrin based porous coordination polymers. / Kim, Hyun Chul; Lee, Young Sun; Huh, Seong; Lee, Suk Joong; Kim, Youngmee.

In: Dalton Transactions, Vol. 43, No. 15, 21.04.2014, p. 5680-5686.

Research output: Contribution to journalArticle

Kim, Hyun Chul ; Lee, Young Sun ; Huh, Seong ; Lee, Suk Joong ; Kim, Youngmee. / CO2 selective 1D double chain dipyridyl-porphyrin based porous coordination polymers. In: Dalton Transactions. 2014 ; Vol. 43, No. 15. pp. 5680-5686.
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AB - Thermal reactions of MnCl(DPyP) (DPyP = 5,15-di(4-pyridyl)-10,20- diphenylporphyrin) as a metalloligand with CoII and ZnII ions in dimethylformamide led to neutral one-dimensional (1D) double chain dipyridyl-porphyrin-based porous coordination polymers (PCPs), Co 3(DPyP)3·4DMF (I) and Zn3(DPyP) 3·2DMF·4H2O (II). Both PCPs were structurally characterized by X-ray crystallography. Particularly, the central MnIII ion in MnCl(DPyP) was transmetallated with CoII or ZnII ions and the central CoII or ZnII ions were further coordinated to pyridyl groups of neighboring M(DPyP) (M = Co or Zn) porphyrin complexes. PCPs I and II are isostructural and each 1D double chain interacts with another 1D double chain by multiple hydrogen bonding to stabilize the resulting framework. Therefore, solvent-free 1D double chain PCPs have permanent porosity, and the void volumes of the solvent-free I and II are calculated to be 22.6% and 23.0%, respectively. Gas sorption analysis indicated that I and II exhibited selective adsorption of CO2 at 196 K. Both PCPs exhibited much smaller sorption abilities for N2 (77 K), H 2 (77 K), and CH4 (196 K) than CO2 (196 K). Both PCPs exhibited different PXRD patterns when dried at 373 K, which indicated that the framework transformation of the isostructural M3(DPyP) 3 type of PCPs strongly depended on the type of central metal ions.

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