Wydział Chemii

Jan Janczak

Daniel Prochowicz

Janusz Lewiński

David Fairen-Jimenez

Tomasz Bereta

Jerzy Lisowski

2016

Chemistry-A European Journal

22

598-609

10.1002/chem.201503479

Naukowa

Angielski

Artykuł

Three zinc(II) ions in combination with two units of enantiopure [3+3] triphenolic Schiff-base macrocycles1,2,3, or4form cage-like chiral complexes. The formation of these complexes is accompanied by the enantioselective self-recognition of chiral macrocyclic units. The X-ray crystal structures of these trinuclear complexes show hollow metal-organic molecules. In some crystal forms, these barrel-shaped complexes are arranged in a window-to-window fashion, which results in the formation of 1D channels and a combination of both intrinsic and extrinsic porosity. The microporous nature of the [Zn₃1₂] complex is reflected in its N₂, Ar, H₂, and CO₂adsorption properties. The N₂and Ar adsorption isotherms show pressure-gating behavior, which is without precedent for any noncovalent porous material. A comparison of the structures of the [Zn₃1₂] and [Zn₃3₂] complexes with that of the free macrocycle H₃1reveals a striking structural similarity. In H₃1, two macrocyclic units are stitched together by hydrogen bonds to form a cage very similar to that formed by two macrocyclic units stitched together by Zn^IIions. This structural similarity is manifested also by the gas adsorption properties of the free H₃1macrocycle. Recrystallization of [Zn₃1₂] in the presence of racemic 2-butanol resulted in the enantioselective binding of (S)-2-butanol inside the cage through the coordination to one of the Zn^IIions.

cage compounds, macrocycles, microporousmaterials, self-recognition, zinc

http://dx.doi.org/10.1002/chem.201503479

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