Self-Organization of 𝐊+-Crown Ether Derivatives into Double-Columnar Arrays Controlled by Supramolecular Isomers of Hydrogen-Bonded Anionic Biimidazolate Ni Complexes

Anionic tris (biimidazolate) nickelate (II) ([Ni(Hbim)3]−), which is a hydrogen-bonding (H-bonding) molecular building block, undergoes self-organization into honeycomb-sheet superstructures connected by complementary intermolecular H-bonds. The crystal obtained from the stacking of these sheets is...

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Bibliographic Details
Main Authors: Makoto Tadokoro, Kyosuke Isoda, Yasuko Tanaka, Yuko Kaneko, Syoko Yamamoto, Tomoaki Sugaya, Kazuhiro Nakasuji
Format: Article
Language:English
Published: Wiley 2012-01-01
Series:Journal of Nanotechnology
Online Access:http://dx.doi.org/10.1155/2012/216050
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Summary:Anionic tris (biimidazolate) nickelate (II) ([Ni(Hbim)3]−), which is a hydrogen-bonding (H-bonding) molecular building block, undergoes self-organization into honeycomb-sheet superstructures connected by complementary intermolecular H-bonds. The crystal obtained from the stacking of these sheets is assembled into channel frameworks, approximately 2 nm wide, that clathrate two cationic K+-crown ether derivatives organised into one-dimensional (1D) double-columnar arrays. In this study, we have shown that all five cationic guest-included crystals form nanochannel structures that clathrate the 1-D double-columnar arrays of one of the four types of K+-crown ether derivatives, one of which induces a polymorph. This is accomplished by adaptably fitting two types of anionic [Ni(Hbim)3]− host arrays. One is a ΔΛ−ΔΛ−ΔΛ⋯ network with H-bonded linkages alternating between the two different optical isomers of the Δ and Λ types with flexible H-bonded [Ni(Hbim)3]−. The other is a ΔΔΔ−ΛΛΛ⋯ network of a racemate with 1-D H-bonded arrays of the same optical isomer for each type. Thus, [Ni(Hbim)3]− can assemble large cations such as K+ crown-ether derivatives into double-columnar arrays by highly recognizing flexible H-bonding arrangements with two host networks of ΔΛ−ΔΛ−ΔΛ⋯ and ΔΔΔ−ΛΛΛ⋯.
ISSN:1687-9503
1687-9511