Accurately tuning the charge on giant polyoxometalate type Keplerates through stoichiometric interaction with cationic surfactants.

We report an approach of exploring the interaction between cationic surfactants and a type of structurally well-defined, spherical "Keplerate" polyoxometalate (POM) macroanionic molecular clusters, {Mo72V30}, in aqueous solution. The effectiveness of the interaction can be determined by monitoring the size change of the "blackberry" supramolecular structures formed by the self-assembly of {Mo72V30} macroions, which is determined by the effective charge density on the macroions. Long-chain surfactants (CTAB and CTAT) can interact with {Mo72V30} macroions stoichiometrically and lower their charge density.

Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution.

We report the self-assembly processes in solution of three Keplerate-type molybdenum-oxide based clusters {Mo72V30}, {Mo72Cr30} and {Mo72Fe30} (all with diameters of approximately 2.5 nm). These clusters behave as unique weak polyprotic acids owing to the external water ligands attached to the non-Mo metal centers.

Charge regulation as a stabilization mechanism for shell-like assemblies of polyoxometalates.

We show that the equilibrium size of single-layer shells composed of polyoxometalate macroions is inversely proportional to the dielectric constant of the medium in which they are dispersed. This behavior is consistent with a stabilization mechanism based on Coulomb repulsion combined with charge regulation. We estimate the cohesive energy per bond between macroions on the shells to be approximately -6kT.

A complete macroion-"blackberry" assembly-macroion transition with continuously adjustable assembly sizes in {Mo132} water/acetone systems.

A complete, continuous transition from discrete macroions to blackberry structures, and then back to discrete macroions, is reported for the first time in the system of {Mo132}/water/acetone, with {Mo132} (full formula (NH4)42[Mo132O372(CH3COO)30(H2O)72].ca.300H2O.

Nanometer-sized molybdenum-iron oxide capsule-surface modifications: external and internal.

The cluster {(Mo)Mo5}12Fe(III)30 1 a present in compound 1 (cluster diameter approximately 2.3 nm), which belongs to the family of nanoscale spherical porous {(Mo)Mo5}12{Linker}30 capsules that allow a new type of nanochemistry inside their cavities as well as unprecedented aggregation processes under gaseous, solution, and solid-state conditions, is the starting material for the present investigation. In solution it reacts with LnCl3 x nH2O (Ln = Ce, Pr) thereby replacing six Fe(III) ions with Ln(III) ions to form compounds 2 (Ce) and 3 (Pr).