Study of the counter cation effects on the supramolecular structure and electronic properties of a dianionic oxamate-based {NIII2} helicate

Página do item simplificado
dc.creatorSimosono, Cintia Almeida
dc.creatorSilva, Rafaela Maria Ribeiro da
dc.creatorCampos, Nathália Rodrigues de
dc.creatorSilva, Marye Agnes Renata
dc.creatorDoriguetto, Antonio Carlos
dc.creatorFlores, Leonã da Silva
dc.creatorCorrea, Charlane Cimini
dc.creatorSimões, Tatiana Renata Gomes
dc.creatorValdo, Ana Karoline Silva Mendanha
dc.creatorMartins, Felipe Terra
dc.date.accessioned2023-12-05T10:50:52Z
dc.date.available2023-12-05T10:50:52Z
dc.date.issued2023-02-23
dc.description.abstractHerein, we describe the synthesis, crystal structure, and electronic properties of {[K2(dmso)(H2O)5][Ni2(H2mpba)3]·dmso·2H2O}n (1) and [Ni(H2O)6][Ni2(H2mpba)3]·3CH3OH·4H2O (2) [dmso = dimethyl sulfoxide; CH3OH = methanol; and H4mpba = 1,3-phenylenebis(oxamic acid)] bearing the [Ni2(H2mpba)3]2− helicate, hereafter referred to as {NiII2}. SHAPE software calculations indicate that the coordination geometry of all the NiII atoms in 1 and 2 is a distorted octahedron (Oh) whereas the coordination environments for K1 and K2 atoms in 1 are Snub disphenoid J84 (D2d) and distorted octahedron (Oh), respectively. The {NiII2} helicate in 1 is connected by K+ counter cations yielding a 2D coordination network with sql topology. In contrast to 1, the electroneutrality of the triple-stranded [Ni2(H2mpba)3] 2− dinuclear motif in 2 is achieved by a [Ni(H2O)6]2+ complex cation, where the three neighboring {NiII2} units interact in a supramolecular fashion through four R22(10) homosynthons yielding a 2D array. Voltammetric measurements reveal that both compounds are redox active (with the NiII/NiI pair being mediated by OH– ions) but with differences in formal potentials that reflect changes in the energy levels of molecular orbitals. The NiII ions from the helicate and the counter-ion (complex cation) in 2 can be reversibly reduced, resulting in the highest faradaic current intensities. The redox reactions in 1 also occur in an alkaline medium but at higher formal potentials. The connection of the helicate with the K+ counter cation has an impact on the energy levels of the molecular orbitals; this experimental behavior was further supported by X-ray absorption near-edge spectroscopy (XANES) experiments and computational calculations.
dc.identifier.citationSIMOSONO, Cintia A. et al. Study of the counter cation effects on the supramolecular structure and electronic properties of a dianionic oxamate-based {NIII2} helicate. Molecules, Basel, v. 28, n. 5, e2086, 2023. DOI: 10.3390/molecules28052086. Disponível em: https://www.mdpi.com/1420-3049/28/5/2086. Acesso em: 30 nov. 2023.
dc.identifier.doi10.3390/molecules28052086
dc.identifier.issne- 1420-3049
dc.identifier.urihttp://repositorio.bc.ufg.br//handle/ri/23886
dc.language.isoeng
dc.publisher.countrySuica
dc.publisher.departmentInstituto de Química - IQ (RMG)
dc.rightsAcesso Aberto
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject{NiII2} helicate
dc.subjectXamate
dc.subjectUpramolecular chemistry
dc.subjectCounter cations
dc.subjectElectronic properties
dc.subjectRedox activity
dc.subjectXANES spectroscopy
dc.subjectTheoretical calculations
dc.titleStudy of the counter cation effects on the supramolecular structure and electronic properties of a dianionic oxamate-based {NIII2} helicate
dc.typeArtigo

Arquivos

Pacote Original
Agora exibindo 1 - 1 de 1
Nenhuma Miniatura disponível
Nome:
Artigo - Cintia Almeida Simosono - 2023.pdf
Tamanho:
2.93 MB
Formato:
Adobe Portable Document Format
Baixar
Licença do Pacote
Agora exibindo 1 - 1 de 1
Nenhuma Miniatura disponível
Nome:
license.txt
Tamanho:
1.71 KB
Formato:
Item-specific license agreed upon to submission
Descrição:
Baixar

Coleções

IQ - Artigos publicados em periódicos