A Novel Hybrid Supramolecular Network Assembled from Perfect π−π Stacking of an Anionic Inorganic Layer and a Cationic Hydronium-Ion-Mediated Organic Layer
✍ Scribed by Tzuoo-Tsair Luo; Yen-Hsiang Liu; Hui-Lien Tsai; Chan-Cheng Su; Chuen-Her Ueng; Kuang-Lieh Lu
- Publisher
- John Wiley and Sons
- Year
- 2004
- Tongue
- English
- Weight
- 182 KB
- Volume
- 2004
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
The synthesis and characterization of a three‐dimensional inorganic‐organic hybrid network [{Cu~2~(CA)~3~}{(H~3~O)~2~(phz)~3~}·G]~n~ (1; H~2~CA = chloranilic acid, phz = phenazine; G = 2CH~3~COCH~3~·2H~2~O) is described. The crystal structure of 1 shows that the 3D network assembly is based on a combination of two types of grid‐building sub‐units of (6,3) topology: an anionic metal‐organic coordination honeycomb grid, and a cationic hydronium‐ion‐mediated organic honeycomb grid. The inorganic and organic honeycomb nets are perfectly π−π‐stacked, creating an infinite number of open‐end channels (channel size about 8 Å in diameter). The solid framework of 1 retains its rigidity upon removal of the guest molecules under high vacuum to form compound [{Cu~2~(CA)~3~}{(H~3~O)~2~(phz)~3~}]~n~ (2) as revealed by a single‐crystal X‐ray diffraction analysis. Compounds [{M~2~(CA)~3~}{(H~3~O)~2~(phz)~3~}·G]~n~ (M = Cd, 3; M = Zn, 4; M = Co, 5; G = 2CH~3~COCH~3~·2H~2~O) were also prepared and characterized as isostructures of 1 [crystal data for 1: Cu~2~(CA)~3~(H~3~O)~2~(phz)~3~·G, trigonal, space group P$\bar 3$
1__m__, formula mass = 1478.86, a = 13.7593(2) Å, c = 9.1869(2) Å, V = 1506.22(5) Å^3^, Z = 1; crystal data for 2: Cu~2~(CA)~3~(H~3~O)~2~(phz)~3~, trigonal, space group P$\bar 3$
1__m__, formula mass = 1326.62, a = 13.7565(4) Å, c = 9.1544(5) Å, V = 1500.3(1) Å^3^, Z = 1]. The magnetic‐exchange coupling between the copper centers for compound 1 was analyzed on the basis of the Curie−Weiss expression and a dinuclear magnetic model. The negative values of the Weiss constant and the magnetic‐exchange coupling constant indicate an antiferromagnetic interaction between the copper centers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)