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Thermal-induced dynamic self-assembly of adenine-grafted polyoxometalate complexes.

Dalton transactions (Cambridge, England : 2003) (2012-05-29)
Zhenfeng He, Yi Yan, Bao Li, Hui Ai, Huanbing Wang, Haolong Li, Lixin Wu
ABSTRACT

A new kind of organic-inorganic hybrid complexes based on polyoxometalate were synthesized through symmetrically grafting two adeninyl groups onto Anderson-type MnMo(6) clusters and encapsulating the clusters by organic surfactants. The resultant complexes exhibited thermal-induced dynamic self-assembly behaviors which greatly depended on the ambient temperature and the chain length of cationic surfactants. With the encapsulation of a short surfactant tetrabutyl ammonium, the complex assembled into fibrous, rod-like, and tubular architectures respectively upon heating; while for the case of using a long surfactant dimethyldioctadecyl ammonium as counter ions, the assemblies of the complex transformed from fibers to spheres with the increased temperature. Moreover, the two types of transformations were both reversible during a cooling process. The related mechanism was investigated by combining multiple characterization methods including X-ray crystallography, XPS, FT-IR and temperature-dependent (1)H NMR, which indicated that such a thermal-induced morphological transformation resulted from a synergy effect of the variation of the multiple hydrogen bonds among the complexes and the rearrangement of the surfactants surrounding the MnMo(6) clusters. These results demonstrated a new concept that hydrogen bonds can be rationally employed as the driving force for the fabrication of polyoxometalate-based materials with smart responsive properties.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Tetrabutylammonium phosphate monobasic solution, 1.0 M in H2O
Sigma-Aldrich
Tetrabutylammonium cyanide, 95%
Sigma-Aldrich
Tetrabutylammonium hydroxide solution, technical, ~40% in H2O (~1.5 M)
Sigma-Aldrich
Tetrabutylammonium perchlorate, ≥95.0% (T)
Sigma-Aldrich
Tetrabutylammonium hydroxide solution, 1.0 M in methanol
Sigma-Aldrich
Tetrabutylammonium hydroxide solution, 40 wt. % in H2O
Sigma-Aldrich
Tetrabutylammonium hydrogensulfate, 97%
Sigma-Aldrich
Tetrabutylammonium hydroxide solution, 54.0-56.0% in H2O
Supelco
Tetrabutylammonium perchlorate, for electrochemical analysis, ≥99.0%
Supelco
Tetrabutylammonium hydroxide solution, ~40% in water, suitable for ion chromatography
Sigma-Aldrich
Tetrabutylammonium cyanide, technical, ≥80%
Supelco
Tetrabutylammonium phosphate monobasic solution, suitable for ion pair chromatography, LiChropur, concentrate, ampule
Sigma-Aldrich
Tetrabutylammonium bisulfate solution, ~55% in H2O
Sigma-Aldrich
Tetrabutylammonium fluoride solution, 75 wt. % in H2O
Sigma-Aldrich
Tetrabutylammonium nitrate, 97%
Sigma-Aldrich
Tetrabutylammonium fluoride solution, 1.0 M in THF
Sigma-Aldrich
Tetrabutylammonium bromide solution, 50 wt. % in H2O
Sigma-Aldrich
Tetrabutylammonium iodide, reagent grade, 98%
Sigma-Aldrich
Tetrabutylammonium bromide, ACS reagent, ≥98.0%
Supelco
Tetrabutylammonium bromide, suitable for ion pair chromatography, LiChropur, ≥99.0%
Sigma-Aldrich
Tetrabutylammonium chloride, ≥97.0% (NT)
Sigma-Aldrich
Tetrabutylammonium bisulfate, puriss., ≥99.0% (T)
Supelco
Tetrabutylammonium iodide, suitable for ion pair chromatography, LiChropur, ≥99.0%
Supelco
Tetrabutylammonium bisulfate, suitable for ion pair chromatography, LiChropur, ≥99.0%
Supelco
Tetrabutylammonium chloride, suitable for ion pair chromatography, LiChropur, ≥99.0%
Sigma-Aldrich
Tetrabutylammonium iodide, ≥99.0% (AT)
Supelco
Tetrabutylammonium bisulfate solution, suitable for ion pair chromatography, LiChropur, concentrate, ampule
Sigma-Aldrich
Tetrabutylammonium phosphate monobasic, puriss., ≥99.0% (T)
Sigma-Aldrich
Tetrabutylammonium azide