Unexpected Solvent-Dependent Self-Assembly of Alkali Metal Complexes of Calix[6]-mono-crown-4: Dinuclear Bowls, a Pseudo- Capsule, and a One-Dimensional
- Authors
- Kim, Seulgi; Lee, Dong Hee; Park, Ki-Min; Jung, Jong Hwa; Lee, Shim Sung; Park, In-Hyeok
- Issue Date
- Nov-2022
- Publisher
- AMER CHEMICAL SOC
- Citation
- INORGANIC CHEMISTRY, v.61, no.45, pp 18213 - 18220
- Pages
- 8
- Indexed
- SCIE
SCOPUS
- Journal Title
- INORGANIC CHEMISTRY
- Volume
- 61
- Number
- 45
- Start Page
- 18213
- End Page
- 18220
- URI
- https://scholarworks.gnu.ac.kr/handle/sw.gnu/29968
- DOI
- 10.1021/acs.inorgchem.2c03020
- ISSN
- 0020-1669
1520-510X
- Abstract
- 1,4-Bridged calix[6]-mono-crown-4 (H4L) capable of metal binding was employed, and the influence of solvent variations on the formation of alkali metal complexes (1-6) was investigated. In the crystal, the bowl-shaped H4L host contains one water molecule in a good-fit fashion via H-bonds. When the H4L host was reacted with alkali metal hydroxides (M = Na, K, Rb, and Cs) in chloroform/ methanol (solvent A), anion-free dinuclear bowl-shaped complexes of type [M2(H2L)] were isolated regardless of the metal ions. In the dinuclear bowl complexes 1-4, two metal ions (M1 and M2) show different binding behaviors: one (M1) locates inside the pocket like an "egg-in-nest", and the other (M2) positions above the M1 interacting with the calix rim. When chloroform/acetonitrile (solvent B) was used in potassium(I) complexation, interestingly, an elegant pseudo-capsule-type quadrunuclear complex 5 was isolated. In 5, two dipotassium(I) bowls in a rim -to-rim arrangement are triply bridged by one water and two acetonitrile molecules like a magic glue. However, in dichloromethane/methanol (solvent C), cesium(I) yielded an infinite product 6 in which dicesium(I) bowls are linked by cation-pi interactions, giving rise to a one-dimensional zigzag coordination polymer. Taken collectively, all products share a dinuclear bowl unit, some of which are further extended to the pseudo-capsule or polymeric array, depending on the solvents. The results suggest the solvent variation as a versatile engineering tool and present a perspective on the metallosupramolecules of calix[6]-mono-crowns with monomer, dimer (e.g., pseudo-capsule), and polymer topologies.
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