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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