Two recent DiMoCat works highlighted by ChemistryWorld

ChemistryWorld has recently highlighted two works of our group:

The jellium model assumes a uniform distribution of positive charge corresponding to the cluster atomic nuclei and their innermost electrons in which the interacting valence electrons move. The energy levels of valence electrons for such a model are 1S21P61D102S21F142P61G182D103S2…, where S, P, D, F, and G letters denote the angular momentum and numbers 1, 2, 3 indicate the radial nodes. The abundance found in experimental mass spectra of alkali, alkaline earth metals, and gold clusters of 2, 8, 18, 20, 34, 40… atoms are justified taken into account that these numbers correspond to closed-shell electronic structures in the jellium model. We have proven that if the last energy level of valence electrons for the jellium model is half-filled with same-spin electrons, the system has also an aromatic character that provides extra stability. This situation is reached for the magic numbers of valence electrons of 1 (S =1/2), 5 (S = 3/2), 13 (S = 5/2), 19 (S = 1/2), 27 (S = 7/2), 37 (S = 3/2), 49 (S = 9/2)… This new set of magic numbers may become a powerful tool for researchers who work in the quest for stable single high-spin molecules for their use as single-molecule based magnets. The paper has been published in Chem. Commun. and can be found in the following link Chem. Commun., 55 (2019) 5559-5562.

In this recent Chem. Commun. paper, we have proved that C18 (a cycle of 18 carbon atoms connected with alternating single and triple bonds) it is an electron acceptor of similar characteristics as C60. C18  when coupled with a range of donor molecules can readily accept electrons. Electron acceptors are important components in molecular electronic devices and solar cells, and, therefore, C18 is added to the list of organic electron acceptors that can be potentially useful in photovoltaics.

Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Cobalt Complexes

The burning of fossil fuels is causing a global climatic emergency. In order to solve this crisis, is very important to improve the efficiency of the production of renewable energies by transforming CO2 into carbon-based fuels. In this report, the member of the DIMOCAT Josep M. Luis in collaboration with the Julio Lloret group, determined the mechanism and bottlenecks of the CO2 reduction reaction with a model cobalt catalyst. The theoretical calculations, in combination with in situ measurements, pinpointed an elusive cobalt(I) carbonyl intermediate, which is formed very early in the reaction and is responsible for one of the most problematic bottlenecks in the CO2 reduction process. The mechanistic studies allowed the identification the bottlenecks of the reaction and the design of a photocatalytic strategy to break the carbonylic compounds  and then strongly improve the efficient of the catalytic reduction of the CO2.

Sergio Fernández, Federico Franco, Carla Casadevall, Vlad Martin-Diaconescu, Josep M. Luis, Julio Lloret-Fillol.

“A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes”

J. Am. Chem. Soc. 2019, ASAP