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- Title
New structure, reconstruction, and behaviour of the coordination polymer framework [CuZn(CN)<sub>4</sub>]--towards hydrated alkali metal ions.
- Authors
Junpei Yamada; Shin-ichi Nishikiori
- Abstract
A new framework structure of the coordination polymer [CuZn(CN)4]- has been discovered in the newly synthesized [Na(H2O)n][CuZn(CN)4] (n = 12.7; 1). X-ray crystal structure analysis revealed a 3D framework comprised of tetrahedral Cu(I) and Zn(II) centres with bridging cyanide ligands containing both octagonal and square channel cavities; these channels contain hydrated Na+ ions as guests. In open air, complex 1 is extremely unstable and loses water molecules to form [Na(H2O)n][CuZn(CN)4] (n = 5.2-6.8; 2) within 30 min. Powder X-ray diffraction patterns showed that this change results in the conversion of the framework of complex 1 to the same framework observed in [K(H2O)n][CuZn(CN)4]. The [CuZn(CN)4]-framework of [K(H2O)n][CuZn(CN)4] has a tridymite structure with hexagonal channel cavities occupied by hydrated K+ ions. Like 1, 2 is also unstable under atmospheric conditions, yielding [Na(H2O)n][CuZn(CN)4] (n = 3), which has an unknown structure. While the framework of [K(H2O)n][CuZn(CN)4] is structurally flexible and robust, the framework of 2 is unstable and fragile. This contrast comes from the difference between the nature of the hydrated K+ and Na+ ions present in the frameworks.
- Subjects
COORDINATION polymers; ALKALI metal ions; CYANIDES; INCLUSION compounds; HYDRATION; X-ray crystallography; LIGANDS (Chemistry)
- Publication
Canadian Journal of Chemistry, 2015, Vol 93, Issue 8, p913
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/cjc-2014-0533