Examinando por Autor "Rojas Poblete, Macarena Gemita"

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    Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re₆(μ₃-Q)₈X₆]⁴- clusters : synthesis and photochemistry
    (Universidad Andrés Bello, 2018) Rojas Poblete, Macarena Gemita; Ramiro Arratia Pérez.; Facultad de Ciencias Exactas
    ehalcogenide compounds of hexarhenium (111), have been extensively studied in recent years, these compounds possess a series of physical and chemical properties, which have been investigated in solid state and in solution. In this line, the new hexarhenium cluster of coordination with 2,6-(dipirid-3-il)-4- cyanophenilpyridine, was synthesized, and a series of tests were carried out to analyze its potentinl use as an antitumoral agent and biomarker, especially due to the interesting fluorescence that presents in the near infra red region (NIR). A Born-Haber thermodynamic cycle was used to determine the redox potential in a series of hexarhenium (111) clusters of the form [Re6(μr0)8X6]4. where Q =s2• and Se 2 • and X = F·, er, Br", r, eN·, Ne·, SeN·, Nes·, OeN· and Neo·. Frequency analysis, relativistic and solvent effects were considered to estimate the free energy of the reversible process Relll6/Re1115 RelV at the DFT level. AII the redox potentials were reported with regards to the standard hydrogen electrode (SHE) and are in reasonable agreement with the available experimental results. In general, the molecular orbitals involved in the redox process were localized in the cluster core [Re6(μ3-Q)8]2\ and therefore the peripheral ligands act only as a modifier of the crystal-field strength, influencing the energy of the frontier molecular orbital splitting. Additionally, the theoretical approach was validated using an experimental protocol to study the electrochemical behavior of the [Re6(μrSe)816]3 " cluster. An important first reversible reduction process was found at E112 = +0.47 V (SHE), which is in good agreement with the value predicted theoretically in this investigation.