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Counter-Ion Association Effect in Dilute Giant Polyoxometalate [AsIII 12CeIII 16(H2O)36W148O524]76−({W148}) and [Mo132O372(CH3COO)30 (H2O)72]42− ({Mo132}) Macroanionic Solutions

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Abstract

This article reports the use of simple conductivity measurements to explore the state of small counter-ions (mostly NH +4 and Na+) in \([\hbox{As}^{\rm III}_{12}\hbox{Ce}^{\rm III}_{16}(\hbox{H}_2\hbox{O})_{36}\hbox{W}_{148}\hbox{O}_{524}]^{76-} (\{\hbox{W}_{148}\})\) and \([\hbox{Mo}_{132}\hbox{O}_{372}(\hbox{CH}_{3}\hbox{COO})_{30} (\hbox{H}_{2}\hbox{O})_{72}]^{42-} (\{\hbox{Mo}_{132}\})\) macroanionic solutions. All the solutions are dialyzed to remove the extra electrolytes. Conductivity measurements on {(NH4)70Na6W148} and {(NH4)42Mo132} solutions at different concentrations both before and after dialysis indicate that the state of counter-ions has obvious concentration dependence. The “counter-ion association” phenomenon, that is, some small counter-ions closely associate with macroanions and move together, has been observed in both types of macroionic solutions above certain concentration. The association of counter-ions in hydrophilic macroionic solutions provides support on our previous speculation that the counter-ions might be responsible for the unique self-assembly of such macroanions into single-layer blackberry-type structures.

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Acknowledgments

T.L. acknowledges support of this work by the National Science Foundation and Lehigh University (startup fund and FRG).

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Authors and Affiliations

  1. Department of Chemistry, Lehigh University, Bethlehem, PA, 18015, USA

    Guang Liu, Melissa L. Kistler, Tong Li, Anish Bhatt & Tianbo Liu

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  1. Guang Liu
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  2. Melissa L. Kistler
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  3. Tong Li
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  4. Anish Bhatt
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  5. Tianbo Liu
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Correspondence to Tianbo Liu.

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Dedicated with sincere regards to Professor Michael Pope on the occasion of his retirement.

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Liu, G., Kistler, M., Li, T. et al. Counter-Ion Association Effect in Dilute Giant Polyoxometalate [AsIII 12CeIII 16(H2O)36W148O524]76−({W148}) and [Mo132O372(CH3COO)30 (H2O)72]42− ({Mo132}) Macroanionic Solutions. J Clust Sci 17, 427–443 (2006). https://doi.org/10.1007/s10876-006-0063-z

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