Issue 22, 2016

Tunable gas adsorption properties of porous coordination polymers by modification of macrocyclic metallic tectons

Abstract

By using the semi-rigid ligand tetrakis[4-(carboxyphenyl)oxamethyl]methane acid (H4TCM) and various macrocyclic metallic tectons, eight new Ni(II) coordination polymers, namely, [(NiL1)2(TCM)]·17H2O (1), [(NiL2)2(TCM)]·17H2O (2), [(NiL3)2(TCM)]·18H2O (3), [(NiL4)2(TCM)]·4DMF·10H2O (4), [(NiL5)2(TCM)]·4DMF·9H2O (5), [(NiL6)2(TCM)]·20H2O (6), [(NiL7)2(TCM)]·18H2O (7), [(NiL8)2(TCM)]·4H2O (8) (L1 = 1,8-dimethyl-1,3,6,8,10,13-hexaaza-cyclotetradecane, L2 = 1,3,6,9,11,14-hexaaza-tricyclooctadecane, L3 = 1,3,6,10,12,15-hexaaza-tricycloeicosane, L4 = 1,3,6,8,11,14-hexaaza-tricyclooctadecane, L5 = 4-methyl-1,3,6,8,11,14-hexaaza-tricyclooctadecane, L6 = 1,3,6,8,12,15-hexaaza-tricycloeicosane, L7 = 11-methyl-1,4,8,10,13,15-hexaaza-tricycloicosane and L8 = 3,10-diisobutyl-1,3,5,8,10,12-hexaaza-cyclotetradecane), were synthesized and structurally characterized. Single crystal X-ray analyses reveal that compounds 1–8 exhibit a similar diamondoid (dia) topology network. Regulated by macrocyclic metallic tectons, compounds 1–3 feature a three-dimensional (3D) framework with 7-fold interpenetration, giving rise to a 1D porous channel with size of ca. 1 nm. Compounds 4–7 possess a 3D network with 2D porous channels (porous size ca. 0.5 nm) and 4-fold interpenetration. Compound 8 shows a 3D dense packing arrangement with 2-fold interpenetration. The porosity of compounds 1–7 was confirmed by N2 gas adsorption measurements at 77 K. Furthermore, due to functional groups exposed on the porous surface, activated compound 3 exhibits selective adsorption of CO2 over N2. The results show the crystal structure, stability and gas adsorption can be tuned by the modification of macrocyclic metallic tectons.

Graphical abstract: Tunable gas adsorption properties of porous coordination polymers by modification of macrocyclic metallic tectons

Supplementary files

Article information

Article type
Paper
Submitted
06 aug 2015
Accepted
13 nov 2015
First published
16 nov 2015

CrystEngComm, 2016,18, 4084-4093

Tunable gas adsorption properties of porous coordination polymers by modification of macrocyclic metallic tectons

X. Jiang, K. Hu and H. Kou, CrystEngComm, 2016, 18, 4084 DOI: 10.1039/C5CE01577D

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