Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re6(μ3-Q)8X6]4− clusters

Rojas-Poblete, Macarena; Carreño, Alexánder; Gacitúa, Manuel; Páez‐Hernández, Dayán; Rabanal‐León, Walter A.; Arratia‐Pérez, Ramiro

doi:10.1039/c7nj05114j

Cited by 11 publications

(9 citation statements)

References 56 publications

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“…Time-dependent density functional theory (R-TDDFT) ( Macleod‐Carey et al, 2018 ) calculations were performed to complement our analysis to elucidate and assign the calculated electronic transitions ( Carreno et al, 2017 ; Rojas-Poblete et al, 2018 ). The calculated UV-Vis spectra in acetonitrile showed two principal absorption bands centered in the range 330–340 nm and 375 nm, in agreement with the experimental data.…”

Section: Resultsmentioning

confidence: 99%

New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE

et al. 2021

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Sodium-dodecyl-sulfate polyacrylamide gel electrophoresis (SDS-PAGE) can be used to separate proteins based mainly on their size such as in denaturing gels. Different staining methods have been reported to observe proteins in the gel matrix, where the most used dyes are generally anionic. Anionic dyes allow for interactions with protonated amino acids, retaining the dye in the proteins. Fluorescent staining is an alternative technique considered to be sensitive, safe, and versatile. Some anionic complexes based on d6 transition metals have been used for this purpose, where cationic dyes have been less explored in this context. In this work, we synthesized and characterized a new monocationic rhenium complex fac-[Re(CO)3(deeb)B2]+ (where deeb is 4,4′-bis(ethoxycarbonyl)-2,2′-bpy and B2 is 2,4-di-tert-butyl-6-(3H-imidazo[4,5-c]pyridine-2-yl)phenol). We carried out a structural characterization of this complex by MS+, FTIR, 1H NMR, D2O exchange, and HHCOSY. Moreover, we carried out UV-Vis, luminescence, and cyclic voltammetry experiments to understand the effect of ligands on the complex’s electronic structure. We also performed relativistic theoretical calculations using the B3LYP/TZ2P level of theory and R-TDDFT within a dielectric continuum model (COSMO) to better understand electronic transitions and optical properties. We finally assessed the potential of fac-[Re(CO)3(deeb)B2]+ (as well as the precursor fac-Re(CO)3(deeb)Br and the free ligand B2) to stain proteins separated by SDS-PAGE. We found that only fac-[Re(CO)3(deeb)B2]+ proved viable to be directly used as a luminescent dye for proteins, presumably due to its interaction with negatively charged residues in proteins and by weak interactions provided by B2. In addition, fac-[Re(CO)3(deeb)B2]+ seems to interact preferentially with proteins and not with the gel matrix despite the presence of sodium dodecyl sulfate (SDS). In future applications, these alternative cationic complexes might be used alone or in combination with more traditional anionic compounds to generate counterion dye stains to improve the process.

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Section: Resultsmentioning

confidence: 99%

New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE

et al. 2021

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“…Moreover, the molecular orbitals involved in the redox process were localized in the cluster core, Re 6 (μ 3 ‐Q 8 ) 2+ , where the peripheral ligands act only as a modifier of the crystal‐field strength, influencing the energy of the frontier molecular orbitals. This theoretical approach was validated by an experimental protocol to study the electrochemical behavior of [Re 6 (μ 3 ‐Se 8 )I 6 ] 3− cluster, where an important first reversible reduction process was found at E 1/2 = +0.47 V (SHE), which is in good agreement with the value predicted theoretically (+0.28 V) …”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…Reproduced from Ref. with permission from the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry…”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…[131] 2.8 | Redox behavior , which is in good agreement with the value predicted theoretically (+0.28 V). [132] 2.9 | Luminescent properties…”

Section: Insights Into Surface-substrate Interactionmentioning

confidence: 99%

“…Reproduced from Ref. [132] with permission from the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry Moreover, the antenna effect in a covalent lanthanide (III) macrocyclic complex was discussed. [115] On the other hand, the antenna effect induced by organometallic chromophores in bimetallic d-f complexes has been well developed by Ferraro and Cantero-Lopez, [143,144]…”

Section: Antenna Effectmentioning

confidence: 99%

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Advances in bonding and properties of inorganic systems from relativistic calculations in Latin America

MacLeod‐Carey

Caramori

Guajardo‐Maturana

et al. 2018

Int J of Quantum Chemistry

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The inclusion of relativistic effects to understand chemical structures and related properties brings to the scientific community challenging study cases, showing the rich diversity of chemical behavior of the different elements along the periodic table. The results highlighted here represent applications of relativistic methodologies to study the nature of bonding and a prediction of optical and magnetic properties of meaningful chemical entities containing heavy atoms, all made in Latin America. The good agreement between calculated and experimental observables in many molecular and cluster‐like systems ratifies that relativistic methods are appropriate to describe these entities realistically. We expect to enhance our knowledge in these methodologies, currently included in doctoral programs in our region.

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Octahedral Chalcogenide Rhenium Clusters: From Solids to Isolated Cluster Complexes

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2019

Structure and Bonding

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Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re₆(μ₃-Q)₈X₆]⁴⁻ clusters

Abstract: A Born–Haber thermodynamic cycle was used to determine the redox potential in a series of rhenium(iii) clusters theoretical analysis at DFT level was considered to estimate the free energy of the reversible process ReIII6/ReIII5ReIV.

Cited by 11 publications

References 56 publications

New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE

New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE

Advances in bonding and properties of inorganic systems from relativistic calculations in Latin America

Octahedral Chalcogenide Rhenium Clusters: From Solids to Isolated Cluster Complexes

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