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Square Grid Metal–Chloranilate Networks as Robust Host Systems for Guest Sorption
Author(s) -
Kingsbury Christopher J.,
Abrahams Brendan F.,
Auckett Josie E.,
Chevreau Hubert,
Dharma A. David,
Duyker Samuel,
He Qilin,
Hua Carol,
Hudson Timothy A.,
Murray Keith S.,
Phonsri Wasinee,
Peterson Vanessa K.,
Robson Richard,
White Keith F.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805600
Subject(s) - square (algebra) , host (biology) , sorption , grid , square tiling , computer science , mathematics , chemistry , ecology , geometry , biology , adsorption , organic chemistry
Reaction of the chloranilate dianion with Y(NO 3 ) 3 in the presence of Et 4 N + in the appropriate proportions results in the formation of (Et 4 N)[Y(can) 2 ], which consists of anionic square‐grid coordination polymer sheets with interleaved layers of counter‐cations. These counter‐cations, which serve as squat pillars between [Y(can) 2 ] sheets, lead to alignment of the square grid sheets and the subsequent generation of square channels running perpendicular to the sheets. The crystals are found to be porous and retain crystallinity following cycles of adsorption and desorption. This compound exhibits a high affinity for volatile guest molecules, which could be identified within the framework by crystallographic methods. In situ neutron powder diffraction indicates a size‐shape complementarity leading to a strong interaction between host and guest for CO 2 and CH 4 . Single‐crystal X‐ray diffraction experiments indicate significant interactions between the host framework and discrete I 2 or Br 2 molecules. A series of isostructural compounds (cat)[M III (X‐an) 2 ] with M=Sc, Gd, Tb, Dy, Ho, Er, Yb, Lu, Bi or In, cat=Et 4 N, Me 4 N and X‐an=chloranilate, bromanilate or cyanochloranilate bridging ligands have been generated. The magnetic properties of representative examples (Et 4 N)[Gd(can) 2 ] and (Et 4 N)[Dy(can) 2 ] are reported with normal DC susceptibility but unusual AC susceptibility data noted for (Et 4 N)[Gd(can) 2 ].