writer：?Zhenfeng He, Yi Yan, Bao Li, Huanbing Wang, Hui Ai, Haolong Li,* Lixin Wu,
keywords：organic-inorganic hybrid complex，dynamic self-assembly，polyoxometalate
source：期刊
specific source：Dalton Trans, 2012, 41, 10043–10051.
Issue time：2012年

A new kind of organic–inorganic hybrid complexes based on polyoxometalate were synthesized through

symmetrically grafting two adeninyl groups onto Anderson-type MnMo6 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 1H 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 MnMo6 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.