Herein, we showh ow the chaotropic effect arising from reduced molybdate ions in acidified aqueous solution is able to amplify drastically weak supramolecular interactions. Time-resolved Small Angle X-rayS cattering (SAXS) analysis suggests that molybdenum-blue oligomeric species form huge aggregates in the presence of g-cyclodextrin (g-CD) which results in the fast formation of nanoscopic {Mo 154 }-based hostguest species,w hile X-ray diffraction analysis reveals that the ending-point of the scenario results in an unprecedented threecomponent well-ordered core-shell-like motif.As imilar arrangement was found by using preformed hexarhenium chalcogenide-type cluster [Re 6 Te 8 (CN) 6 ] 4À as exogenous guest. This seminal work brings better understanding of the selfassembly processes in general and gives new opportunities for practical applications in the design of complex multicomponent materials via the simplicity of the non-covalent chemistry.
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