Reversible and Vapochromic Chemisorption of Ammonia by a Copper(ii) Coordination Polymer

The single crystal X-ray structure determination of {[Cu(tpt)(o-phthalate)]·31/3(C2H2Cl4)}n (tpt?=?2,4,6-tri-4-pyridyl-1,3,5-triazine, C2H2Cl4?=?1,1,2,2-tetrachloroethane?=?TCE) shows a 3D network in which CuII centres are linked by 3-connecting tpt ligands with the topology of a 12,3 net. CuII cent...

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Bibliographic Details
Published in:Critical studies in media communication 2019-01, Vol.72 (10), p.817
Main Authors: Wegeberg, Christina, Nielsen, David, Mossin, Susanne, Abrahams, Brendan F, McKee, Vickie, McKenzie, Christine J
Format: Article
Language:English
Subjects:
Acetone
Ammonia
Anions
Basal plane
Chemisorption
Chemistry
Coordination polymers
Copper
Copper compounds
Crystal structure
Crystallinity
Desorption
Electron paramagnetic resonance
Phthalates
Pyridines
Single crystals
Topology
X ray powder diffraction
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Summary:The single crystal X-ray structure determination of {[Cu(tpt)(o-phthalate)]·31/3(C2H2Cl4)}n (tpt?=?2,4,6-tri-4-pyridyl-1,3,5-triazine, C2H2Cl4?=?1,1,2,2-tetrachloroethane?=?TCE) shows a 3D network in which CuII centres are linked by 3-connecting tpt ligands with the topology of a 12,3 net. CuII centres are further linked by o-phthalate dianions. The copper coordination geometry is square pyramidal, with o-phthalate oxygen donors trans to each other in the basal plane and the remaining positions taken by the pyridines of three linking tpt units. The solvent accessible void space is ~65?%. The pale blue-green crystalline desolvate, obtained by heating to 200°C or washing the TCE solvate with acetone is formulated as [Cu(tpt)(o-phthalate)]n. Powder X-ray diffraction and electron paramagnetic resonance spectroscopy show that the crystal structure and the CuII geometry changes upon desolvation. The crystalline desolvated phase sorbs two equivalents of ammonia per copper ion. The adduct, mauve [Cu(tpt)(o-phthalate)(NH3)2]n, shows reasonable crystallinity and is stable up to ~150°C under ambient conditions before the reversible desorption (minimum 10 cycles) of the guest ammonia. The colour change and high desorption temperature, along with changes in g values, is suggestive of chemisorption in two steps with Cu-ammine bonding in the loaded phase.
ISSN:1529-5036
DOI:10.1071/CH19264