Assessment of the electronic structure of a triruthenium acetate-pyridylnaphthalimide cluster

Mateus, Douglas Braz Gonçalves; Souza, Sâmya da Silva; Silva, Ricardo Junior de Bacchi; Batista, Ana Paula de Lima; Cicolani, Renato Salviato; Murie, Valter E.; Nishimura, Rodolfo Hideki Vicente; Clososki, Giuliano C.; Oliveira-Filho, Antonio G. S. de; Demets, Grégoire Jean-François; Nikolaou, Sofia

doi:10.1016/j.jphotochem.2020.112361

Cited by 8 publications

(6 citation statements)

References 55 publications

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“…The results presented are similar to those published by us previously 25 and similar to those recently published by Nikolaou and collaborators 22 for this class of compounds. However, to go forward and study the gold nanoparticle hybrid, it is fundamental to perform the analysis of the electronic properties of the cluster complex for each excitation wavelength, which was performed by TDDFT calculations to obtain the resonance Raman spectra of the complex.…”

Section: ■ Results and Discussionsupporting

confidence: 92%

“…As can be seen in Table 1, the HOMO orbitals of the complex are localized in the ruthenium ions and acetate ligands, consistent with the previously described model proposed by Mayer and collaborators. 22,25,37,42 The LUMO orbitals have a mixed composition where the lowest energy MO is more located in the ruthenium ions (LUMO) but there is a shift to the terpyridine (LUMO+1, LUMO+2, and LUMO +3) and pyridines (LUMO+4) in the next higher energy empty orbitals.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Oxo–triruthenium acetate clusters or just triruthenium clusters are well-known for their electrochemical properties and spectroelectrochemical properties, where it is possible to modulate their absorption employing electrochemical potential. − Recently, this class of compounds was subject to relevant publications in several areas such as transport and release of nitric oxide and anticancer activity, electrochromic and catalytic properties, − and we have been studying the interaction of triruthenium clusters on electrodes and with gold nanoparticles. ,, …”

Section: Introductionmentioning

confidence: 99%

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Unveiling Anomalous Surface-Enhanced Resonance Raman Scattering on an Oxo–Triruthenium Acetate Cluster Complex by a Theoretical–Experimental Approach

et al. 2020

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Surface-enhanced Raman spectroscopy (SERS) has been explored by the most diverse areas of research over the past 40 years, with more special attention from analytical chemistry. Although there is a great consensus that there are two mechanisms that contribute most to the observation of the phenomenon (electromagnetic (EM) and charge transfer (CT)), several anomalies are observed, especially when studying complexes of transition metals. In this article, we present a theoretical and experimental study of Raman and SERS of an oxo–triruthenium acetate cluster ([Ru3O (CH3COO)6(py)2(pytpy)]), where it was possible to observe one of these “anomalies” of the SERS effect, in this case, an unexpected enhancement of the vibrational stretching mode of the oxo group. This cluster had its electrochemical and spectroelectrochemical properties studied by cyclic voltammetry and electronic spectroscopy in the visible and near-infrared, where it was possible to observe the fully reversible waves of the ruthenium sites (separated by 1.00 V) and the terpyridinic ligand and how the absorption of this complex varies drastically when reduced electrochemically. The molecular orbitals and electronic transitions of this cluster were calculated by time-dependent density-functional theory (TDDFT), where it can be noted that the HOMO orbitals are almost exclusively composed of the atomic orbitals of ruthenium and the LUMO orbitals can be composed of a mixture of ruthenium orbitals and acetate ligands, as well as terpyridine. From the TDDFT calculations and the transitions energies obtained, the complex resonant Raman and Raman spectra were simulated using different excitation wavelengths (696, 785, and 1064 nm), where an unexpected intensification of oxygen stretching at the Ru3O center at 700 cm–1 was observed considering the excitation at 785 nm, even though there was no expected transition. The experimental SERS spectra of the complex in two redox states (Ru3 III, III, III and Ru3 III, III, II) were obtained experimentally using gold and silver nanoparticles with an excitation wavelength laser at 785 nm, where a very intense signal at 700 cm–1, for the Ru3 III, III, II redox state, was observed. The simulation of electronic states by TDDFT and SERS spectra by DFT, considering an Au20 cluster adduct, showed an intensification of the entire complex, with great emphasis on the Ru3O center and the 700 cm–1 mode that, however, was not as intense as the results obtained experimentally, indicating an anomalous intensification.

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Section: ■ Results and Discussionsupporting

confidence: 92%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Unveiling Anomalous Surface-Enhanced Resonance Raman Scattering on an Oxo–Triruthenium Acetate Cluster Complex by a Theoretical–Experimental Approach

et al. 2020

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“…1,8-Naphthalimides (NI) represent a large family of compounds that are easily tunable and highly thermally and chemically stable. Their well-known photophysical properties makes them ideal candidates to be explored in different real-life applications such as the production of organic photochemical dyads and triads, energy storage, light conversion, gels, hybrid materials, optoelectronic devices, solar cells, sensors, biological applications, and bioimaging probes among others [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 ].…”

Section: Introductionmentioning

confidence: 99%

Using Room Temperature Phosphorescence of Gold(I) Complexes for PAHs Sensing

et al. 2021

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The synthesis of two new phosphane-gold(I)–napthalimide complexes has been performed and characterized. The compounds present luminescent properties with denoted room temperature phosphorescence (RTP) induced by the proximity of the gold(I) heavy atom that favors intersystem crossing and triplet state population. The emissive properties of the compounds together with the planarity of their chromophore were used to investigate their potential as hosts in the molecular recognition of different polycyclic aromatic hydrocarbons (PAHs). Naphthalene, anthracene, phenanthrene, and pyrene were chosen to evaluate how the size and electronic properties can affect the host:guest interactions. Stronger affinity has been detected through emission titrations for the PAHs with extended aromaticity (anthracene and pyrene) and the results have been supported by DFT calculation studies.

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“…Espectro eletrônico de absorção no UV-vis qualitativo para o cluster Mãe em metanol e as atribuições das bandas observadas Figura 30 -(A) Estrutura do cluster mãe otimizada no nível de teoria BP86-D3(BJ)/def2-TZVP (B) Espectro eletrônico de absorção na região do UV-vis para o cluster mãe, calculado via TD-DFT (C) NTOs envolvidos nas duas principais transições observadas, com os devidos pesos na resultante calculadaFonte:(MATEUS;SOUZA; …”

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>i<N>/i<-(4-piridil)-1,8-naftalimida e sua combinação com um cluster trinuclear de rutênio: síntese, caracterização e investigação espectroscópica

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Em um período de grande desmonte da educação e desvalorização dos Professores, dedico este meu primeiro agradecimento a todos os professores que participaram da minha formação, desde o jardim até o presente momento. Agradeço por todo conhecimento a mim transmitido, e por me mostrarem não só o quanto é prazeroso aprender, mas também o quão amável é a tarefa de compartilhar o conhecimento com o próximo. Um agradecimento mais que especial a minha orientadora, Profª Sofia Nikolaou: um grande exemplo de Mulher, Professora, Pesquisadora, Orientadora e Amiga. É incrível como você é capaz de desempenhar com maestria todos esses papéis. Não consigo resumir em palavras o quão grato, orgulhoso e honrado eu me sinto por ter a oportunidade de trilhar o caminho da ciência ao seu lado, tendo como horizonte um dos melhores exemplos que eu já encontrei. Na ausência dessas palavras, um obrigado nunca teve uma carga de significado tão intensa. Obrigado! A toda minha família, em especial a minha mãe Marli, meu pai Antônio, minha avó Joana, minha irmã Fernanda e meu cunhado Gustavo por todo o amor, suporte e confiança em mim investidos. Obrigado por me acompanharem por todas as etapas desta longa caminhada, por me motivarem e me acolherem nos bons e maus momentos. Vocês são o motivo de eu sempre seguir em frente! Ao meu companheiro, Luiz Gustavo, por todo amor, carinho, compreensão e apoio ao longo de toda a duração do mestrado. Obrigado por ser meu porto seguro, por me ouvir e por compartilhar suas experiências de pós-graduação, não me deixando desanimar no meio do caminho.

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Assessment of the electronic structure of a triruthenium acetate-pyridylnaphthalimide cluster

Cited by 8 publications

References 55 publications

Unveiling Anomalous Surface-Enhanced Resonance Raman Scattering on an Oxo–Triruthenium Acetate Cluster Complex by a Theoretical–Experimental Approach

Unveiling Anomalous Surface-Enhanced Resonance Raman Scattering on an Oxo–Triruthenium Acetate Cluster Complex by a Theoretical–Experimental Approach

Using Room Temperature Phosphorescence of Gold(I) Complexes for PAHs Sensing

>i<N>/i<-(4-piridil)-1,8-naftalimida e sua combinação com um cluster trinuclear de rutênio: síntese, caracterização e investigação espectroscópica

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