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Angew Chem Int Ed Engl. 2018 Apr 3;57(15):4067-4072. doi: 10.1002/anie.201800409. Epub 2018 Mar 5.

Effect of Cation-π Interaction on Macroionic Self-Assembly.

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Department of Polymer Science, University of Akron, Akron, OH, 44325, USA.
Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China.
X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439, USA.
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, 60115, USA.
Material Science Division, Argonne National Laboratory, Argonne, IL, 60439, USA.
Department of Chemistry, University of Akron, Akron, OH, 44325, USA.


A series of rod-shaped polyoxometalates (POMs) [Bu4 N]7 [Mo6 O18 NC(CH2 O)3 MnMo6 O18 (OCH2 )3 CNMo6 O18 ] and [Bu4 N]7 [ArNMo6 O17 NC(CH2 O)3 MnMo6 O18 (OCH2 )3 CNMo6 O17 NAr] (Ar=2,6-dimethylphenyl, naphthyl and 1-methylnaphthyl) were chosen to study the effects of cation-π interaction on macroionic self-assembly. Diffusion ordered spectroscopy (DOSY) and isothermal titration calorimetry (ITC) techniques show that the binding affinity between the POMs and Zn2+ ions is enhanced significantly after grafting aromatic groups onto the clusters, leading to the effective replacement of tetrabutylammonium counterions (TBAs) upon the addition of ZnCl2 . The incorporation of aromatic groups results in the significant contribution of cation-π interaction to the self-assembly, as confirmed by the opposite trend of assembly size vs. ionic strength when compared with those without aromatic groups. The small difference between two aromatic groups toward the Zn2+ ions is amplified after combining with the clusters, which consequently triggers the self-recognition behavior between two highly similar macroanions.


binding affinity; cation-π interaction; macroionic self-assembly; polyoxometalates; self-recognition


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