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Water de/adsorption associated with single‐crystal‐to‐single‐crystal structural transformation of a series of two‐dimensional metal–organic frameworks, [M(bipy)(C 4 O 4 )(H 2 O) 2 ]·3H 2 O (M = Mn (1), Fe (2), and Zn (3), and bipy=4,4′‐bipyridine)
Author(s) -
Wang ChihChieh,
Ke SzuYu,
Hsieh YiFang,
Huang ShihTing,
Wang TzuHeng,
Lee GeneHsiang,
Chuang YuChun
Publication year - 2019
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201900170
Subject(s) - chemistry , squaric acid , crystallography , single crystal , supramolecular chemistry , molecule , octahedron , crystal structure , adsorption , metal organic framework , metal , denticity , thermogravimetric analysis , metal ions in aqueous solution , powder diffraction , organic chemistry
An assembly of three metal coordination polymers (CPs), [M(bipy)(C 4 O 4 )(H 2 O) 2 ]·3H 2 O (M = Mn ( 1 ), Fe ( 2 ), Zn ( 3 ), and bipy = 4,4′‐bipyridine, C 4 O 4 2− (squarate) = dianion of H 2 C 4 O 4 (squaric acid)), was synthesized and structurally characterized. Single‐crystal X‐ray structural determination reveals that compounds 1 – 3 are iso‐structural, in which the M(II) ions are six‐coordinate in a distorted octahedral geometry. C 4 O 4 2− and bipy both act as bridging ligands with bis ‐monodentate coordination mode connecting the M(II) ions to form a two‐dimensional (2D) layered metal–organic framework (MOF). Adjacent 2D layers are then arranged in parallel and interpenetrated manners to construct their three‐dimensional (3D) supramolecular architecture. Compounds 1 , 2 , and 3 undergo two‐step dehydration processes with the first and second weight losses of 14.1 and 8.6% for 1 , of 12.1 and 7.5% for 2, and of 11.2 and 8.1% for 3 , respectively, corresponding to the weight losses of the three guest water molecules and the two coordinated water molecules, and all exhibit reversible sponge‐like water de/adsorption properties during de/rehydration processes for guest water molecules as per cyclic thermogravimetric analysis (TGA). The single‐crystal‐to‐single‐crystal (SCSC) structural transformation during the reversible de/rehydration processes of three guest water molecules was identified and monitored using exhaustive single‐crystal and powder X‐ray diffraction measurements.