title: The role of the [CpM(CO)2](-) chromophore in the optical properties of the [Cp2ThMCp(CO)2](+) complexes, where M = Fe, Ru and Os. A theoretical view.
abstract: The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2](+) complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2](-) chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.
authors.affiliation: Relativistic Molecular Physics (ReMoPh) Group, Ph.D. Program in Molecular Physical Chemistry, Universidad Andrés Bello, Av. República 275, Santiago 8370146, Chile. dayan.paez@unab.cl.
authors.forename: Plinio
authors.initials: P
authors.lastname: Cantero-López
authors.affiliation: Institut des Sciences Chimiques de Rennes UMR CNRS 6226, Université de Rennes 1, 35042 Rennes, France.
authors.forename: Laura
authors.initials: L
authors.lastname: Le Bras
authors.affiliation: Relativistic Molecular Physics (ReMoPh) Group, Ph.D. Program in Molecular Physical Chemistry, Universidad Andrés Bello, Av. República 275, Santiago 8370146, Chile. dayan.paez@unab.cl and Núcleo Milenio de Ingeniería Molecular para Catálisis y Biosensores, ICM, Chile.
authors.forename: Dayán
authors.initials: D
authors.lastname: Páez-Hernández
authors.affiliation: Relativistic Molecular Physics (ReMoPh) Group, Ph.D. Program in Molecular Physical Chemistry, Universidad Andrés Bello, Av. República 275, Santiago 8370146, Chile. dayan.paez@unab.cl and Núcleo Milenio de Ingeniería Molecular para Catálisis y Biosensores, ICM, Chile.
authors.forename: Ramiro
authors.initials: R
authors.lastname: Arratia-Pérez
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D004396:Coloring Agents / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D009992:Osmium / Q000737:chemistry*; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D004396:Coloring Agents; D056831:Coordination Complexes; D008024:Ligands; D002245:Carbon Dioxide; D009992:Osmium; D012428:Ruthenium; D007501:Iron