%0 Journal Article
%T Self-Organization of -Crown Ether Derivatives into Double-Columnar Arrays Controlled by Supramolecular Isomers of Hydrogen-Bonded Anionic Biimidazolate Ni Complexes
%A Makoto Tadokoro
%A Kyosuke Isoda
%A Yasuko Tanaka
%A Yuko Kaneko
%A Syoko Yamamoto
%A Tomoaki Sugaya
%A Kazuhiro Nakasuji
%J Journal of Nanotechnology
%D 2012
%I Hindawi Publishing Corporation
%R 10.1155/2012/216050
%X Anionic tris (biimidazolate) nickelate (II) ([Ni(Hbim)3]ˋ), 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 2ˋnm 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]ˋ host arrays. One is a 忖 托 ˋ 忖 托 ˋ 忖 托 ˋ network with H-bonded linkages alternating between the two different optical isomers of the 忖 and 托 types with flexible H-bonded [Ni(Hbim)3]ˋ. The other is a 忖 忖 忖 ˋ 托 托 托 ˋ network of a racemate with 1-D H-bonded arrays of the same optical isomer for each type. Thus, [Ni(Hbim)3]ˋ 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 忖 托 ˋ 忖 托 ˋ 忖 托 ˋ and 忖 忖 忖 ˋ 托 托 托 ˋ . 1. Introduction Self-assembled supramolecular architectures are currently of considerable interest owing to their intriguing network topologies and their potential applications in microelectronics, nonlinear optics, porous materials, and other technologies [1每10]. A tenet of crystal engineering, which belongs to supramolecular chemistry as well, is to control multidimensional network topologies in crystals constructed from molecular building blocks that are connected by means of mutual interactions of H-bonds and metal-coordination bonds [11每26]. For example, three-dimensional (3-D) molecular networks such as complicated (10,3)-a and (10,3)-b nets in crystals can also be produced in the field of crystal engineering by a rational design of artificial molecular building blocks [27每43]. In a previous report, we showed that 2,2∩-biimidazolate monoanions (Hbimˋ) was convenient for fabricating, via one-pot self-organization, controlled crystal structures that are not only coordinated to a transition metal ion but also connected to each other through intermolecular H-bonds of the complementary dual N-HˋN type [44每50]. The self-organizing superstructures formed from the H-bonded networks of the transition metal complexes with Hbimˋ can be controlled in
%U http://www.hindawi.com/journals/jnt/2012/216050/