Synthesis, characterization and photoelectrochemical performance of a tris-heteroleptic ruthenium(II) complex having 4,7-dimethyl-1,10-phenanthroline

Mechanistic Insights into the Stepwise Assembly of Ruthenium(II) Tris-heteroleptic Compounds

“…Only when the methoxy substituent was used were the spectral changes distinct from the other substituents, characterized by an increase in absorbance of the lowest-energy band and the formation of a partially insoluble product. Absorption spectra registered at the end of reactions are very similar to those observed for the isolated cis-[Ru(R-phen)(dcbH 2 )(NCS) 2 ] compounds (R = H, Me, and Ph), 21 indicating their formation as the major product in this step. Absorption changes (545−585 nm) as a function of time were fitted by a sum of two exponential functions, indicating the occurrence of simultaneous reactions.…”

“…32 The isothiocyanate isomer can be isolated from the isomer mixture by liquid chromatography. 21,22 cis-[Ru(phen)(dcbH 2 )-(NCS) 2 ] was prepared and purified by this method, and thus it was possible to obtain only the N-bound isomer. Considering that both associative and dissociative substitution mechanisms can occur in the rate-determining step, the rate law can be written as a function of the concentration of the precursor ruthenium(II) species [Ru(p-cymene)(DMF)-Cl] + and two terms: k D , concerning a dissociative mechanism, and [R-phen] multiplied by k A , concerning an associative mechanism, as shown in eq 1.…”

“…In the second step, dcbH 2 is added, and the temperature is A mixture of N-and S-bounded isomers is usually obtained, which can be further separated by using liquid chromatography with Sephadex LH-20 as the stationary phase and methanol or DMF as the mobile one. 21,22 Although this one-pot route is widely disseminated for the development of new ruthenium(II) tris-heteroleptic compounds, each of its individual steps has not yet been extensively investigated. A deep understanding of the effects of temperature, reaction time, and ligand structure may be a useful tool to guide the adjustment of synthetic conditions to increase product yields, reduce the formation of byproducts, and shorten the total time of synthesis.…”

A importância do estado excitado 3MLCT de compostos de Ru(II), Re(I) e Ir(III) no desenvolvimento de fotossensores, OLEDS e fotorredução de CO2

“…A primeira consiste na conversão direta de energia solar em eletricidade, por exemplo, utilizando células solares sensibilizadas por corantes. [143][144][145][146][147][148][149][150][151][152][153][154][155] A segunda estratégia consiste na sua conversão em energia química, através de processos redutivos e da formação de ligações químicas, [156][157][158][159][160][161][162][163] inspirada pelo processo fotossintético natural, no qual certos organismos que usam o CO 2 da atmosfera e a água como reagentes para produzir carboidratos e outros produtos de carbono concomitantemente à geração de oxigênio molecular, Equação 3.…”

Síntese e caracterização de complexos polipiridínicos de Ru(II) com diferentes ligantes carboxilatos e avaliação da reatividade frente ao oxigênio molecular

“…x 10 -3 mol L -1 em diclorometano em solução eletrolítica 0,1 mol L -1 de TBAPF 6 2 (acpy)] + com concentração de 2,9 x 10 -3 mol L -1 a 10 mV s -1 em diclorometano em solução eletrolítica 0,1 mol L -1 de TBAPF 6 2 (acpy)] + com concentração de 2,9 x 10 -3 mol L -1 a 100 mV s -1 em diclorometano em solução eletrolítica 0,1 mol L -1 de TBAPF 6 WHANG e APAYDIN, 2018), corantes sensibilizadores em células solares (GRÄTZEL, 2003;2005;GONG et al, 2012;CARVALHO et al, 2014), OLEDs (Organic Light-Emitting Diodes, Diodos Emissores de Luz Orgânicos) (FANTACCI e DE ANGELIS, 2011;WONG et al, 2014;KIM et al, 2015;SUZUKI et al, 2015), catalisadores em reações de compostos orgânicos (ZENG et al, 2008;PRIER et al, 2013;BEATTY e STEPHENSON, 2015;SHAW et al, 2016), interruptores moleculares (GÜTLICH et al, 2001;LIN et al, 2011;MERINO e RIBAGORDA, 2012;PATROCINIO et al, 2013), polímeros (JANIAK, 2003ROBIN e FROMM, 2006), marcadores celulares (STOEFFLER et al, 1995;FERNANDEZ-MOREIRA et al, 2010;YE et al, 2016), entre outros. Dentre as propriedades dos compostos de coordenação destaca-se a (foto)reatividade frente a reações de transferência eletrônica.…”