TY - JOUR
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
N1 - Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.
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.
UR - http://www.scopus.com/inward/record.url?scp=84893708644&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84893708644&partnerID=8YFLogxK
U2 - 10.1021/cg401583v
DO - 10.1021/cg401583v
M3 - Article
AN - SCOPUS:84893708644
VL - 14
SP - 699
EP - 704
JO - Crystal Growth and Design
JF - Crystal Growth and Design
SN - 1528-7483
IS - 2
ER -