Interpenetration control, sorption behavior, and framework flexibility in Zn(II) metal-organic frameworks

Ji Hye Park; Woo Ram Lee; Yeonga Kim; Hye Jin Lee; Dae Won Ryu; Won Ju Phang; Chang Seop Hong

doi:10.1021/cg401583v

Interpenetration control, sorption behavior, and framework flexibility in Zn(II) metal-organic frameworks

Ji Hye Park, Woo Ram Lee, Yeonga Kim, Hye Jin Lee, Dae Won Ryu, Won Ju Phang, Chang Seop Hong

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

38 Citations (Scopus)

Abstract

Three Zn(II) frameworks [Zn(H₂L)(bdc)]·1.4DEF·0. 6H₂O (1; H₂L = 1,4-di(1H-imidazol-4-yl)benzene, H ₂bdc = terephthalic acid), [Zn(H₂L)(bdc)]·1. 5DMF·1.2H₂O (2), and [Zn(H₂L)(L) _0.5(bdc)_0.5]·formamide·H₂O (3) were prepared under the solvothermal conditions in DEF/H₂O, DMF/H₂O, and formamide/H₂O solvent pairs, respectively. All compounds are commonly based on the adamantanoid three-dimensional networks that are mutually entangled to form a 3-fold (1) to 4-fold (2) to 5-fold interpenetrating dia structure (3). The solvent pairs used in the reactions are primarily responsible for the variation of such interpenetration degree. It is noted that the reaction time, temperature, and reactant ratio applied in the present system (2) did not lead to the interpenetration change. The activated sample (1a) shows the gas uptake of N₂, H₂, and CO ₂, characteristic of permanent porosity in the flexible framework, while the gases of N₂ and H₂ are not adsorbed on 2 and 3. The porous compound (1) also exhibits the reversible inclusion and release of I₂ in MeOH. Interestingly, 2 reveals the reversible structural transformation during the activation-resolvation process where the solid can be activated through two routes (solvent exchange/desolvation and direct desolvation). However, there is no appreciable structural flexibility upon solvent exchange in 3 with 5-fold interpenetration, indicating that this framework is more robust, compared to 1 and 2 with lower interpenetration degrees.

Original language	English
Pages (from-to)	699-704
Number of pages	6
Journal	Crystal Growth and Design
Volume	14
Issue number	2
DOIs	https://doi.org/10.1021/cg401583v
Publication status	Published - 2014 Feb 5

ASJC Scopus subject areas

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

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@article{6edc45bc54784db390b3330345ae1d5b,

title = "Interpenetration control, sorption behavior, and framework flexibility in Zn(II) metal-organic frameworks",

abstract = "Three Zn(II) frameworks [Zn(H2L)(bdc)]·1.4DEF·0. 6H2O (1; H2L = 1,4-di(1H-imidazol-4-yl)benzene, H 2bdc = terephthalic acid), [Zn(H2L)(bdc)]·1. 5DMF·1.2H2O (2), and [Zn(H2L)(L) 0.5(bdc)0.5]·formamide·H2O (3) were prepared under the solvothermal conditions in DEF/H2O, DMF/H2O, and formamide/H2O solvent pairs, respectively. All compounds are commonly based on the adamantanoid three-dimensional networks that are mutually entangled to form a 3-fold (1) to 4-fold (2) to 5-fold interpenetrating dia structure (3). The solvent pairs used in the reactions are primarily responsible for the variation of such interpenetration degree. It is noted that the reaction time, temperature, and reactant ratio applied in the present system (2) did not lead to the interpenetration change. The activated sample (1a) shows the gas uptake of N2, H2, and CO 2, characteristic of permanent porosity in the flexible framework, while the gases of N2 and H2 are not adsorbed on 2 and 3. The porous compound (1) also exhibits the reversible inclusion and release of I2 in MeOH. Interestingly, 2 reveals the reversible structural transformation during the activation-resolvation process where the solid can be activated through two routes (solvent exchange/desolvation and direct desolvation). However, there is no appreciable structural flexibility upon solvent exchange in 3 with 5-fold interpenetration, indicating that this framework is more robust, compared to 1 and 2 with lower interpenetration degrees.",

author = "Park, {Ji Hye} and Lee, {Woo Ram} and Yeonga Kim and Lee, {Hye Jin} and Ryu, {Dae Won} and Phang, {Won Ju} and Hong, {Chang Seop}",

year = "2014",

month = feb,

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doi = "10.1021/cg401583v",

language = "English",

volume = "14",

pages = "699--704",

journal = "Crystal Growth and Design",

issn = "1528-7483",

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T1 - Interpenetration control, sorption behavior, and framework flexibility in Zn(II) metal-organic frameworks

AU - Park, Ji Hye

AU - Lee, Woo Ram

AU - Kim, Yeonga

AU - Lee, Hye Jin

AU - Ryu, Dae Won

AU - Phang, Won Ju

AU - Hong, Chang Seop

PY - 2014/2/5

Y1 - 2014/2/5

N2 - Three Zn(II) frameworks [Zn(H2L)(bdc)]·1.4DEF·0. 6H2O (1; H2L = 1,4-di(1H-imidazol-4-yl)benzene, H 2bdc = terephthalic acid), [Zn(H2L)(bdc)]·1. 5DMF·1.2H2O (2), and [Zn(H2L)(L) 0.5(bdc)0.5]·formamide·H2O (3) were prepared under the solvothermal conditions in DEF/H2O, DMF/H2O, and formamide/H2O solvent pairs, respectively. All compounds are commonly based on the adamantanoid three-dimensional networks that are mutually entangled to form a 3-fold (1) to 4-fold (2) to 5-fold interpenetrating dia structure (3). The solvent pairs used in the reactions are primarily responsible for the variation of such interpenetration degree. It is noted that the reaction time, temperature, and reactant ratio applied in the present system (2) did not lead to the interpenetration change. The activated sample (1a) shows the gas uptake of N2, H2, and CO 2, characteristic of permanent porosity in the flexible framework, while the gases of N2 and H2 are not adsorbed on 2 and 3. The porous compound (1) also exhibits the reversible inclusion and release of I2 in MeOH. Interestingly, 2 reveals the reversible structural transformation during the activation-resolvation process where the solid can be activated through two routes (solvent exchange/desolvation and direct desolvation). However, there is no appreciable structural flexibility upon solvent exchange in 3 with 5-fold interpenetration, indicating that this framework is more robust, compared to 1 and 2 with lower interpenetration degrees.

AB - Three Zn(II) frameworks [Zn(H2L)(bdc)]·1.4DEF·0. 6H2O (1; H2L = 1,4-di(1H-imidazol-4-yl)benzene, H 2bdc = terephthalic acid), [Zn(H2L)(bdc)]·1. 5DMF·1.2H2O (2), and [Zn(H2L)(L) 0.5(bdc)0.5]·formamide·H2O (3) were prepared under the solvothermal conditions in DEF/H2O, DMF/H2O, and formamide/H2O solvent pairs, respectively. All compounds are commonly based on the adamantanoid three-dimensional networks that are mutually entangled to form a 3-fold (1) to 4-fold (2) to 5-fold interpenetrating dia structure (3). The solvent pairs used in the reactions are primarily responsible for the variation of such interpenetration degree. It is noted that the reaction time, temperature, and reactant ratio applied in the present system (2) did not lead to the interpenetration change. The activated sample (1a) shows the gas uptake of N2, H2, and CO 2, characteristic of permanent porosity in the flexible framework, while the gases of N2 and H2 are not adsorbed on 2 and 3. The porous compound (1) also exhibits the reversible inclusion and release of I2 in MeOH. Interestingly, 2 reveals the reversible structural transformation during the activation-resolvation process where the solid can be activated through two routes (solvent exchange/desolvation and direct desolvation). However, there is no appreciable structural flexibility upon solvent exchange in 3 with 5-fold interpenetration, indicating that this framework is more robust, compared to 1 and 2 with lower interpenetration degrees.

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DO - 10.1021/cg401583v

M3 - Article

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JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 2

ER -

Interpenetration control, sorption behavior, and framework flexibility in Zn(II) metal-organic frameworks

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