Understanding polyoxometalates as water oxidation catalysts through iron cobalt reactivity.

Cobalt polyoxometalates (Co-POMs) have emerged as promising water oxidation catalysts (WOCs), with the added advantage of their molecular nature despite being metal oxide fragments. In comparison with metal oxides, that do not offer well-defined active surfaces, POMs have a controlled, discrete structure that allows for precise correlations between experiment and computational analyses. Thus, beyond highly active WOCs, POMs are also model systems to gain deeper mechanistic understanding on the oxygen evolution reaction (OER).

An Ultra-Long-Lived Triplet Excited State in Water at Room Temperature: Insights on the Molecular Design of Tridecafullerenes.

Suitably engineered molecular systems exhibiting triplet excited states with very long lifetimes are important for high-end applications in nonlinear optics, photocatalysis, or biomedicine. We report the finding of an ultra-long-lived triplet state with a mean lifetime of 93 ms in an aqueous phase at room temperature, measured for a globular tridecafullerene with a highly compact glycodendrimeric structure. A series of three tridecafullerenes bearing different glycodendrons and spacers to the C units have been synthesized and characterized.

Formation of C-C(11188)Cl: A Particularly Stable Non-IPR Fullerene.

Halogenation has been one of the most used strategies to explore the reactivity of empty carbon cages. In particular, the higher reactivity of non-IPR fullerenes, i.e.

Unusual C -Symmetric trans-1-(Bis-pyrrolidine)-tetra-malonate Hexa-Adducts of C : The Unexpected Regio- and Stereocontrol Mediated by Malonate-Pyrrolidine Interaction.

A totally unanticipated regio- and stereoisomerically pure C -symmetric trans-1-(bis-pyrrolidine)-tetra-malonate hexa-adduct of C was obtained via a topologically controlled method, followed by a 1,3-dipolar cycloaddition reaction. The structures of the products were elucidated by H and C NMR and by X-ray crystallography. The unexpected regio- and stereoselectivity observed, supported by theoretical calculations, was found to be a consequence of malonate-pyrrolidine interactions.

Different Factors Govern Chlorination and Encapsulation in Fullerenes: The Case of C66.

C66 is one of the smallest fullerenes that is able to encapsulate more than one metal atom, as in Sc2@C66, as well as to get chlorinated at a low level, C66Cl10 or C66Cl6. We show here, with the help of computations at density functional theory level, that these two means of obtaining derivatives of non-isolated pentagon rule fullerenes are dictated by different factors. Chlorination takes place at temperatures lower than 2000 K, once the neutral fullerenes are formed.