TY - JOUR
T1 - Gas Sorption Properties of a New Three-Dimensional In-ABDC MOF With a Diamond Net
AU - Choi, In Hwan
AU - Yoon, Suk Bin
AU - Jang, So Young
AU - Huh, Seong
AU - Kim, Sung Jin
AU - Kim, Youngmee
N1 - Publisher Copyright:
© Copyright © 2019 Choi, Yoon, Jang, Huh, Kim and Kim.
PY - 2019/9/10
Y1 - 2019/9/10
N2 - The pseudotetrahedral node, [In(O2CR)4]−, often found in InIII-based metal-organic frameworks (MOFs) without a cluster-based secondary building unit (SBU) is a negatively charged center due to charge mismatch between an 8-coordinate InIII ion and four anionic carboxylate bridging ligands. Thus, In-MOFs with this pseudotetrahedral node tend to bear a counter-cation near each InIII center in the frameworks. Generally, dialkylammonium-based cations such as Me2NH+2 and Et2NH+2 directly derived from N,N-dimethylformamide (DMF) or N,N-diethylformamide (DEF) solvents during MOF formation reactions play a significant role to form a stable framework through charge matching. If these cations thermally derived from DMF or DEF were not suitable for crystal growth of In-MOFs, it becomes very challenging to obtain high quality single crystals for X-ray structure determination of the frameworks. In this context, high quality crystals of In-ABDC MOF were not easily prepared from a ditopic azobenzene-4,4'-dicarboxylic acid (H2ABDC) through a thermal reaction in DMF or DEF. We successfully overcome this problem by employing a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), and the resulting three-dimensional (3D) In-ABDC MOF, [EMIM][In(ABDC)2]·DEF·H2O (I), was structurally characterized by X-ray diffraction. The 3D framework indicates a 4-connected uninodal net with Schläfli symbol of 66 (dia). The gas sorption properties of solvent-free I were also investigated in detail.
AB - The pseudotetrahedral node, [In(O2CR)4]−, often found in InIII-based metal-organic frameworks (MOFs) without a cluster-based secondary building unit (SBU) is a negatively charged center due to charge mismatch between an 8-coordinate InIII ion and four anionic carboxylate bridging ligands. Thus, In-MOFs with this pseudotetrahedral node tend to bear a counter-cation near each InIII center in the frameworks. Generally, dialkylammonium-based cations such as Me2NH+2 and Et2NH+2 directly derived from N,N-dimethylformamide (DMF) or N,N-diethylformamide (DEF) solvents during MOF formation reactions play a significant role to form a stable framework through charge matching. If these cations thermally derived from DMF or DEF were not suitable for crystal growth of In-MOFs, it becomes very challenging to obtain high quality single crystals for X-ray structure determination of the frameworks. In this context, high quality crystals of In-ABDC MOF were not easily prepared from a ditopic azobenzene-4,4'-dicarboxylic acid (H2ABDC) through a thermal reaction in DMF or DEF. We successfully overcome this problem by employing a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), and the resulting three-dimensional (3D) In-ABDC MOF, [EMIM][In(ABDC)2]·DEF·H2O (I), was structurally characterized by X-ray diffraction. The 3D framework indicates a 4-connected uninodal net with Schläfli symbol of 66 (dia). The gas sorption properties of solvent-free I were also investigated in detail.
KW - azobenzene-4,4'-dicarboxylic acid
KW - carbon dioxide sorption
KW - hydrogen sorption
KW - indium
KW - metal-organic framework
UR - http://www.scopus.com/inward/record.url?scp=85072888482&partnerID=8YFLogxK
U2 - 10.3389/fmats.2019.00218
DO - 10.3389/fmats.2019.00218
M3 - Article
AN - SCOPUS:85072888482
SN - 2296-8016
VL - 6
JO - Frontiers in Materials
JF - Frontiers in Materials
M1 - 218
ER -