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

Fingerprint

Sorption
Gases
Porphyrins
Isotherms
X ray crystallography
Desorption
Thermodynamic properties
Adsorption

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Gas Sorption Properties of Isostructural Co-MOFs Containing Dipyridylporphyrin Linkers with Different Substituents at the 10,20-meso-Positions. / Choi, In Hwan; Chae, Seung Hyun; Huh, Seong; Lee, Suk Joong; Kim, Sung Jin; Kim, Youngmee.

In: European Journal of Inorganic Chemistry, Vol. 2015, No. 18, 01.06.2015, p. 2989-2995.

Research output: Contribution to journalArticle

@article{62cb382d95b341d4be6222651627d2c2,
title = "Gas Sorption Properties of Isostructural Co-MOFs Containing Dipyridylporphyrin Linkers with Different Substituents at the 10,20-meso-Positions",
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.",
keywords = "Carbon dioxide, Cobalt, Gas sorption, Metal-organic frameworks, Porphyrins",
author = "Choi, {In Hwan} and Chae, {Seung Hyun} and Seong Huh and Lee, {Suk Joong} and Kim, {Sung Jin} and Youngmee Kim",
year = "2015",
month = "6",
day = "1",
doi = "10.1002/ejic.201500294",
language = "English",
volume = "2015",
pages = "2989--2995",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",
number = "18",

}

TY - JOUR

T1 - Gas Sorption Properties of Isostructural Co-MOFs Containing Dipyridylporphyrin Linkers with Different Substituents at the 10,20-meso-Positions

AU - Choi, In Hwan

AU - Chae, Seung Hyun

AU - Huh, Seong

AU - Lee, Suk Joong

AU - Kim, Sung Jin

AU - Kim, Youngmee

PY - 2015/6/1

Y1 - 2015/6/1

N2 - 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.

AB - 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.

KW - Carbon dioxide

KW - Cobalt

KW - Gas sorption

KW - Metal-organic frameworks

KW - Porphyrins

UR - http://www.scopus.com/inward/record.url?scp=85027916905&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85027916905&partnerID=8YFLogxK

U2 - 10.1002/ejic.201500294

DO - 10.1002/ejic.201500294

M3 - Article

AN - SCOPUS:85027916905

VL - 2015

SP - 2989

EP - 2995

JO - Chemische Berichte

JF - Chemische Berichte

SN - 0009-2940

IS - 18

ER -