Exploring the Hidden Constraints that Control the Self-Assembly of Nanomolecular Inorganic Clusters

The mechanism that controls the self-assembly of complex polyoxometalate inorganic clusters in solution is a challenge because can contain anywhere from 6 to 368 metal ions single molecule and are commonly assembled under ʻone-potʼ reaction conditions. Furthermore, harnessing ʻself-assemblyʼ processes allows synthesis on length-scale with degree complexity which not easily accessed by more traditional ʻstep-wiseʼ routes. This class molecules important as they be thought ʻmolecular oxidesʼ rival size proteins yet based upon simple MOx units (where M Mo, W, V sometimes Nb x 4, 5, or 7). Here we review structures molybdenum-based then show how it possible only control architectures but explore formation invoking mechanisms normally found biological systems. We describe salt spontaneously form ʻinformation-richʼ, autocatalytic sets replicating work via molecular recognition [PMo12O40]3–, {PMo12} Keggin ion, [Mo36O112(H2O)16]8–, {Mo36} cluster. These small involved an network, where assembly gigantic molybdenum blue wheels [Mo154O462H14(H2O)70]14– {Mo154}, [Mo132O372(H2O)72(CH3CO2)30]42–, {Mo132} ball containing 154 132 templated smaller themselves able catalyze their own formation. Finally, introduce theory used constraints need present facilitate large explain information theoretic arguments might useful for designing highly functional unsymmetrical molecules.