2026-04-18T20:09:07Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/68232022-08-31T00:05:23Zcom_10259_4354com_10259_5086com_10259_2604com_10259_4363col_10259_4355col_10259_4364

Merillas, Beatriz 5693a4a7-6435-43f0-8dbe-628c5f957e9b 500 Cuéllar, Elena 95e50988-4f54-4e44-8802-bc0534b2d036 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. 4fba3e38-8889-454b-842d-c73dc982b21e 600 Miguel, Daniel 5b04d422-8916-42aa-ad97-208de7609bdc 600 Villafañe, Fernando 0398b255-5aef-4584-b325-f2a79a7ae15a 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 IM Thumbnail image/jpeg 3851 https://riubu.ubu.es/bitstream/10259/6823/3/Merillas-ic_2020.pdf.jpg 493f9bea66a6bcf2922fc8a18861a0cd MD5 3 LICENSE license.txt license.txt text/plain; charset=utf-8 998 https://riubu.ubu.es/bitstream/10259/6823/2/license.txt aa90105e1c90a1b4fe810649aa967b7d MD5 2 ORIGINAL Merillas-ic_2020.pdf Merillas-ic_2020.pdf application/pdf 742353 https://riubu.ubu.es/bitstream/10259/6823/1/Merillas-ic_2020.pdf c5b1d904664e765f99c18479f511054f MD5 1 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 RWwgYXV0b3IgY29tbyDDum5pY28gdGl0dWxhciBkZSBsb3MgZGVyZWNob3MgZGUgcHJvcGllZGFkIGludGVsZWN0dWFsIGRlIGxhIG9icmEsIG8gZGlzcG9uaWVuZG8gZGUgbG9zIGRlYmlkb3MgcGVybWlzb3MgZGUgbG9zIG90cm9zIHRpdHVsYXJlcywgc2kgbG9zIGh1YmllcmEsIHkgZW4gdmlydHVkIGRlIGxvcyBkZXJlY2hvcyBxdWUgbGUgY29uZmllcmUgbGEgbGVnaXNsYWNpw7NuIHZpZ2VudGUgc29icmUgcHJvcGllZGFkIGludGVsZWN0dWFsIHkgZGVyZWNob3MgZGUgYXV0b3IsIA0KQVVUT1JJWkEgYSBsYSBVbml2ZXJzaWRhZCBkZSBCdXJnb3MgYSBkaWZ1bmRpciwgZGUgbWFuZXJhIGdyYXR1aXRhLCBlbCBjb250ZW5pZG8gZGUgbG9zIGFyY2hpdm9zIGRpZ2l0YWxlcyBxdWUgY29ycmVzcG9uZGVuIGFsIGRvY3VtZW50byBkZXNjcml0byBhbnRlcmlvcm1lbnRlLCBjb24gY2Fyw6FjdGVyIG5vIGV4Y2x1c2l2byB5IGRlIG1hbmVyYSBww7pibGljYSBlbiBhY2Nlc28gYWJpZXJ0byBhIHRyYXbDqXMgZGUgSW50ZXJuZXQsIHBhcmEgbG8gcXVlIGxhIEJpYmxpb3RlY2EgcHJvY2VkZXLDoSBhIGFyY2hpdmFybG9zIGVuIGVsIFJlcG9zaXRvcmlvIEluc3RpdHVjaW9uYWwuIEFzaW1pc21vIGF1dG9yaXphIGEgbGEgVW5pdmVyc2lkYWQgZGUgQnVyZ29zIGEgcmVhbGl6YXIgbGFzIHRyYW5zZm9ybWFjaW9uZXMgbmVjZXNhcmlhcyBkZSBmb3JtYXRvLCBubyBkZSBjb250ZW5pZG8sIHBhcmEgZ2FyYW50aXphciBsYSBwcmVzZXJ2YWNpw7NuIHkgZWwgYWNjZXNvIGVuIGVsIGZ1dHVyby4NCg0KRWwgYXV0b3IgZGlzcG9uZSwgZW4gdG9kbyBjYXNvLCBkZWwgZGVyZWNobyBhIHJldm9jYXIgZXN0YSBhdXRvcml6YWNpw7NuLg0KDQpMYSBjZXNpw7NuIGRlIGRlcmVjaG9zIGRlIGVzdGEgb2JyYSBzZSBlbmN1ZW50cmEgc3VqZXRhIGEgbGEgbGVnaXNsYWNpw7NuIHZpZ2VudGUgc29icmUgcHJvcGllZGFkIGludGVsZWN0dWFsIHkgZGVyZWNob3MgZGUgYXV0b3I=