TY - JOUR
T1 - Polymorphous Al-MOFs Based on V-Shaped Linker Molecules
T2 - Synthesis, Properties, and in Situ Investigation of Their Crystallization
AU - Krüger, Martin
AU - Inge, A. Ken
AU - Reinsch, Helge
AU - Li, Yuan Han
AU - Wahiduzzaman, Mohammad
AU - Lin, Chia Her
AU - Wang, Sue Lein
AU - Maurin, Guillaume
AU - Stock, Norbert
N1 - Funding Information:
The authors acknowledge support by the group of Prof. Dr. Wolfgang Bensch for the in situ equipment made available and DESY, Hamburg Germany, for the provided beamtime. M.W. and G.M. thank the ANR CHESDENS (ANR-13-SEED-0001-01). A.K.I. is supported by the Knut and Alice Wallenberg Foundation (KAW) through the MAX IV postdoctoral scholarship under the grant number KAW 2012.0363 and also by the Rontgen-Angstrom Cluster (VR) through the MATsynCELL project. This work was financially supported by the Deutsche Forschungsgemeinschaft (DFG) (STO 643/10-1).
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/5/15
Y1 - 2017/5/15
N2 - The in situ and systematic high-throughput investigation of the system Al3+/4,4′-benzophenonedicarboxylic acid (H2BPDC)/DMF/H2O in the presence of various additives was carried out, and a new Al-MOF of composition [Al(OH)(BPDC)], denoted as CAU-21-BPDC, was obtained. Its crystal structure was determined from single-crystal X-ray diffraction data (space group I422, a = b = 17.2528(7) Å, c = 23.864(1) Å). The structure is built up by octanuclear rings of cis corner-sharing AlO6 polyhedra forming the inorganic building unit (IBU). These {Al8O8} IBUs are arranged in a bcu packing and connected via BPDC2- ions in a way that each IBU is linked via two linker molecules to each of the eight adjacent IBUs. Thus, accessible, one-dimensional modulated pores with a diameter between 3.6 and 6.5 Å are formed. In addition, tetrahedral cavities are formed by the BPDC2- linker molecules. The framework of CAU-21-BPDC is polymorphous with that of CAU-8-BPDC, which contains one-dimensional chains of trans corner-sharing AlO6 polyhedra connected by BPDC2- ions. Replacing H2BPDC by 4,4′-oxydibenzoic acid (H2ODB), which contains an oxygen atom between the phenyl rings instead of a keto group, leads to the synthesis of Al-MOFs isoreticular with CAU-8-BPDC and CAU-21-BPDC. In addition, a coordination polymer, [Al(HODB)2(OH)], was discovered and structurally characterized. The structure of CAU-8-ODB was refined from powder X-ray diffraction data, while a Pawley refinement was carried out for CAU-21-ODB to determine the lattice parameters and confirm phase purity. The structure of CAU-21-ODB was confirmed using density functional theory (DFT) calculations. A thorough characterization shows that the CAU-8 and CAU-21-type structures are stable up to 350 and 300 °C in air, respectively, almost independent of the linker molecules incorporated. The former MOFs are porous toward N2 and CO2, while the latter only adsorb CO2.
AB - The in situ and systematic high-throughput investigation of the system Al3+/4,4′-benzophenonedicarboxylic acid (H2BPDC)/DMF/H2O in the presence of various additives was carried out, and a new Al-MOF of composition [Al(OH)(BPDC)], denoted as CAU-21-BPDC, was obtained. Its crystal structure was determined from single-crystal X-ray diffraction data (space group I422, a = b = 17.2528(7) Å, c = 23.864(1) Å). The structure is built up by octanuclear rings of cis corner-sharing AlO6 polyhedra forming the inorganic building unit (IBU). These {Al8O8} IBUs are arranged in a bcu packing and connected via BPDC2- ions in a way that each IBU is linked via two linker molecules to each of the eight adjacent IBUs. Thus, accessible, one-dimensional modulated pores with a diameter between 3.6 and 6.5 Å are formed. In addition, tetrahedral cavities are formed by the BPDC2- linker molecules. The framework of CAU-21-BPDC is polymorphous with that of CAU-8-BPDC, which contains one-dimensional chains of trans corner-sharing AlO6 polyhedra connected by BPDC2- ions. Replacing H2BPDC by 4,4′-oxydibenzoic acid (H2ODB), which contains an oxygen atom between the phenyl rings instead of a keto group, leads to the synthesis of Al-MOFs isoreticular with CAU-8-BPDC and CAU-21-BPDC. In addition, a coordination polymer, [Al(HODB)2(OH)], was discovered and structurally characterized. The structure of CAU-8-ODB was refined from powder X-ray diffraction data, while a Pawley refinement was carried out for CAU-21-ODB to determine the lattice parameters and confirm phase purity. The structure of CAU-21-ODB was confirmed using density functional theory (DFT) calculations. A thorough characterization shows that the CAU-8 and CAU-21-type structures are stable up to 350 and 300 °C in air, respectively, almost independent of the linker molecules incorporated. The former MOFs are porous toward N2 and CO2, while the latter only adsorb CO2.
UR - http://www.scopus.com/inward/record.url?scp=85019460804&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85019460804&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.7b00202
DO - 10.1021/acs.inorgchem.7b00202
M3 - Article
C2 - 28453264
AN - SCOPUS:85019460804
SN - 0020-1669
VL - 56
SP - 5851
EP - 5862
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 10
ER -