title: Unveiling the Reactivity of a Synthetic Mimic of the Oxygen Evolving Complex.
abstract: We simulated for the first time the oxygen-oxygen bond formation in a synthetic calcium-tetra manganese complex recently developed by Zhang and co-workers. In spite of promising structural similarities to the native oxygen evolving complex (OEC) in Photosystem II, several uncertainties on the mimic stability in water and on its potential catalytic activity still persist. Here, we characterized at density functional theory level the electronic and structural features of the Snstates of the complex, along with the oxygen-oxygen bond formation reaction, proposing a reasonable model for the hydrate complex. As a main finding, both the synthetic compound and the natural OEC show very close energetic barriers for the oxo-oxyl coupling process, suggesting that key electronic features of the natural OEC reactivity are well reproduced. This result strongly encourages the use of this synthetic complex in combination with other molecular assemblies for the design of successful artificial leaves.
authors.affiliation: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario di M. S. Angelo , via Cintia, I-80126 Napoli, Italy.
authors.forename: Umberto
authors.initials: U
authors.lastname: Raucci
authors.affiliation: Laboratoire d' Electrochimie, Chimie des Interfaces et Modelisation pour l' Energie, CNRS UMR-7575, Chimie ParisTech , 11 rue P. et M. Curie, F-75231 Paris Cedex 05, France.|Ecole Nationale Supérieure de Chimie de Paris, Chimie ParisTech , 11 rue P. et M. Curie, F-75231 Paris Cedex 05, France.
authors.forename: Ilaria
authors.initials: I
authors.lastname: Ciofini
authors.affiliation: Ecole Nationale Supérieure de Chimie de Paris, Chimie ParisTech , 11 rue P. et M. Curie, F-75231 Paris Cedex 05, France.|Institut Universitaire de France , 103 Bd Saint-Michel, F-75005 Paris, France.
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo
authors.affiliation: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario di M. S. Angelo , via Cintia, I-80126 Napoli, Italy.|Italian Institute of Technology, IIT@CRIB Center for Advanced Biomaterials for Healthcare, Largo Barsanti e Matteucci, I-80125 Napoli, Italy.
authors.forename: Nadia
authors.identifier: http://orcid.org/0000-0002-2983-766X
authors.initials: N
authors.lastname: Rega