TY - JOUR
T1 - Functionalization in flexible porous solids
T2 - Effects on the pore opening and the host-guest interactions
AU - Devic, Thomas
AU - Horcajada, Patricia
AU - Serre, Christian
AU - Salles, Fabrice
AU - Maurin, Guillaume
AU - Moulin, Béatrice
AU - Heurtaux, Daniela
AU - Clet, Guillaume
AU - Vimont, Alexandre
AU - Grenéche, Jean Marc
AU - Le Ouay, Benjamin
AU - Moreau, Florian
AU - Magnier, Emmanuel
AU - Filinchuk, Yaroslav
AU - Marrot, Jerôme
AU - Lavalley, Jean Claude
AU - Daturi, Marco
AU - Férey, Gérard
PY - 2010
Y1 - 2010
N2 - The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF3, -CH3, -NH2, -OH, -CO2H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and 57Fe Mössbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF3)2) exhibits a nitrogen accessible porosity (SBET ≈ 100 m2 g-1). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.
AB - The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF3, -CH3, -NH2, -OH, -CO2H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and 57Fe Mössbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF3)2) exhibits a nitrogen accessible porosity (SBET ≈ 100 m2 g-1). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.
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U2 - 10.1021/ja9092715
DO - 10.1021/ja9092715
M3 - Article
C2 - 20038143
AN - SCOPUS:76149137263
SN - 0002-7863
VL - 132
SP - 1127
EP - 1136
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -