2024-03-28T22:45:05Zhttps://riubu.ubu.es/oai/requestoai:riubu.ubu.es:10259/68232022-08-31T00:05:23Zcom_10259_4354com_10259_5086com_10259_2604com_10259_4363col_10259_4355col_10259_4364
Merillas, Beatriz
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500
Cuéllar, Elena
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500
Diez Varga, Alberto
9c89e938-e737-4d26-8670-1597cd80ae7a
600
Torroba Pérez, Tomás
554
600
García Herbosa, Gabriel
205
600
0000-0002-2863-1272
Fernández, Sergio
48e0a136-0f22-4f71-bf20-928cb706b0e4
Lloret-Fillol, Julio
69534020-c033-49bb-b24e-a09798389bd4
Martín-Alvarez, Jose M.
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600
Miguel, Daniel
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600
Villafañe, Fernando
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600
2022-08-30T11:31:00Z
2022-08-30T11:31:00Z
2020-07
0020-1669
http://hdl.handle.net/10259/6823
10.1021/acs.inorgchem.0c01654
1520-510X
Cationic fac-[Re(CO)3(pz*H)(pypzH)]OTf (pz*H = pyrazole, pzH; 3,5-dimethylpyrazole, dmpzH; indazole, indzH; 3-(2-pyridyl)pyrazole, pypzH) were obtained from fac-[ReBr(CO)3(pypzH)] by halide abstraction with AgOTf and subsequent addition of the corresponding pyrazole. Successive deprotonation with Na2CO3 and NaOH gave neutral fac-[Re(CO)3(pz*H)(pypz)] and anionic Na{fac-[Re(CO)3(pz*)(pypz)]} complexes, respectively. Cationic fac-[Re(CO)3(pz*H)(pypzH)]OTf, neutral complexes fac-[Re(CO)3(pz*H)(pypz)], and fac-[Re(CO)3(pypz)2Na] were subjected to photophysical and electrochemical studies. They exhibit phosphorescent decays from a prevalently 3MLCT excited state with quantum yields (Φ) in the range between 0.03 and 0.58 and long lifetimes (τ from 220 to 869 ns). The electrochemical behavior in Ar atmosphere of cationic and neutral complexes indicates that the oxidation processes assigned to ReI → ReII occurs at lower potentials for the neutral complex compared to cationic complex. The reduction processes occur at the ligands and do not depend on the charge of the complexes. The electrochemical behavior in CO2 saturated media is consistent with CO2 electrocatalyzed reduction, where the values of the catalytic activity [icat(CO2)/icat(Ar)] ranged from 2.7 to 11.5 (compared to 8.1 for fac-[Re(CO)3Cl(bipy)] studied as a reference). Controlled potential electrolysis for the pyrazole cationic (3a) and neutral (4a) complexes after 1 h affords CO in faraday yields of 61 and 89%, respectively. These values are higher for indazole complexes and may be related to the acidity of the coordinated pyrazole.
Spanish MINECO, Spain (PGC2018-099470–B-I00) and Junta de Castilla y León (VA130618), and the authors in Burgos gratefully acknowledge financial support from the Junta de Castilla y León, Consejería de Educación y Cultura y Fondo Social Europeo (Project BU263P18). E.C. thanks the UVa for her grant. We also thank the ICIQ Foundation, AGAUR 2017-SGR-1647 (J.L.-F.) and the Spanish MINECO (CTQ2016-80038-R; J.L-F.), and the Spanish Ministry of Science is acknowledged for a FPU fellowship to S.F.
application/pdf
eng
American Chemical Society
Inorganic Chemistry. 2020, V. 59, n. 15, p. 11152–11165
https://doi.org/10.1021/acs.inorgchem.0c01654
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-099470-B-I00/ES/APLICACION DE MOLECULAS NANOGRAFENICAS EN LA MEJORA DE LAS PROPIEDADES OPTOLELECTRONICAS DE CELULAS SOLARES ORGANICAS
info:eu-repo/grantAgreement/Junta de Castilla y León//VA130618
info:eu-repo/grantAgreement/Junta de Castilla y León//BU263P18
info:eu-repo/grantAgreement/AGAUR//2017-SGR-1647
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-80038-R/ES/REDUCIONES QUIMICAS MEDIADAS POR LA LUZ. DE COMBUSTIBLES A COMPUESTOS SOLARES
Deprotonation
Diimides
Electrodes
Ligands
Reaction mechanisms
Química inorgánica
Chemistry, Inorganic
Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
info:eu-repo/semantics/openAccess
Inorganic Chemistry
59
15
11152
11165
THUMBNAIL
Merillas-ic_2020.pdf.jpg
Merillas-ic_2020.pdf.jpg
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https://riubu.ubu.es/bitstream/10259/6823/3/Merillas-ic_2020.pdf.jpg
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LICENSE
license.txt
license.txt
text/plain; charset=utf-8
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https://riubu.ubu.es/bitstream/10259/6823/2/license.txt
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ORIGINAL
Merillas-ic_2020.pdf
Merillas-ic_2020.pdf
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https://riubu.ubu.es/bitstream/10259/6823/1/Merillas-ic_2020.pdf
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10259/6823
oai:riubu.ubu.es:10259/6823
2022-08-31 02:05:23.954
Repositorio Institucional de la Universidad de Burgos
bubrep@ubu.es
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