Síntese e caracterização de complexos de rutênio com ligante derivado da 9-Hidroxifenalenona

Orientador: Dr. Herbert WinnischoferCoorientador: Eduard WestphalDissertação (mestrado) - Universidade Federal do Paraná, Setor de Ciências Exatas, Programa de Pós-Graduação em Química. Defesa : Curitiba, 27/09/2018Inclui referências: p. 117-127Resumo: No presente trabalho e apresentada a sintese e caracterizacao de um novo derivado da 9-hidroxifenalenona e a coordenacao desse ligante aos complexos derivados de ?6-arenorutenio(II) e 2,2'-bisbipiridinarutenio. O novo ligante 9??hidroxi?? 1??oxo??1H??fenalen??5??carboxilato de metila (L) foi sintetizado com sucesso e caracterizado por espectroscopias de RMN de 1H, 13C e HMBC, FTIR, UV-vis e espectrometria de massa, os quais confirmaram a pureza e a estrutura proposta. O ligante L tambem foi estudado por voltametria ciclica e por espectroeletroquimica UV-vis, na qual apresentou um processo eletroquimico reversivel. Os complexos [Ru(bpy)2L]PF6 e [(?6-C6H6)RuLCl] foram sintetizados a partir da reacao entre L e os respectivos precursores de rutenio. A caracterizacao estrutural dos complexos obtidos foi realizada por DRX de monocristal e espectroscopia de RMN de 1H. No caso do complexo [Ru(bpy)2L]PF6, foi tambem feita a espectrometria de massa de alta resolucao. Para auxiliar nos estudos espectroscopicos de UV-vis e FTIR, voltametria ciclica e espectroeletroquimica UV-vis, calculos teoricos de DFT foram realizados para a determinacao dos orbitais moleculares de L e de ambos os complexos. O complexo [Ru(bpy)2L]PF6 apresentou 4 processos eletroquimicos, sendo tres reversiveis e um irreversivel. Ja o complexo [(?6-C6H6)RuLCl] apresentou quatro processos eletroquimicos irreversiveis. Por fim o complexo [Ru(bpy)2L]PF6 foi utilizado na confeccao de filmes mistos de Langmuir e Langmuir-Blodgett com acido estearico. Os filmes [RuII(bpy)2L]-SA e [RuIII(bpy)2L]-SA apresentaram baixa area molecular indicando uma alta compactacao dos filmes. Alem disso, os filmes apresentaram efeito de histerese no ensaio de compressao-descompressao. Os filmes LB foram caracterizados por espectroscopia IRRAS, a qual indicou que o acido estearico se encontra em uma orientacao proxima ao plano do substrato. Medidas de espectroscopia UV-vis mostraram pouca interacao entre os cromoforos. Por fim, os filmes tambem foram estudados por voltametria ciclica e mostraram um processo eletroquimico reversivel atribuido ao par RuIII/II. Palavras-chave: Complexos de rutenio. 9-hidroxifenalenona. Filmes de Langmir- Blodgett. Acido estearico.Abstract: This work presents the synthesis and characterization of a new ligand derived from the 9-hydroxiphealenone molecule and its association with metal complexes derived from ?6-areneruthenium(II) and 2,2'-bisbipiridineruthenium. The new ligand named 9-hydroxi-1-oxo-1H-phenalen-5-methyl carboxialte (L) was successfully synthesized and characterized via 1H, 13C and HMBC NMR, FTIR, UVvisible spectroscopies and mass spectrometry, which confirmed its purity and structure. Cyclic voltammetry and UV-visible spectroelectrochemical studies were also performed with the ligand L, where a single reversible electrochemical process was observed. The complexes [Ru(bpy)2L]PF6 and [(?6-C6H6)RuLCl] were synthesized from the reaction between L and the metal precursors. The structural characterization of the obtained complexes was made by single crystal X-ray diffraction, as well as by 1H NMR spectroscopy. For the complex [Ru(bpy)2L]PF6, high resolution mass spectrometry was also made. In order to support the spectroscopy and electrochemistry studies, DFT calculations were performed to obtain the molecular orbitals of L and both ruthenium complexes obtained. The [Ru(bpy)2L]PF6 complex presented four electrochemical processes of which three are reversible and one irreversible. The [(?6-C6H6)RuLCl] complex showed four irreversible processes. Also, the [Ru(bpy)2L]PF6 complexes were used mixed with stearic acid in the confection of Langmuir and Langmuir-Blodgett films. The films [RuII(bpy)2L]-SA and [RuIII(bpy)2L]-SA presented low molecular area, indicative of a high compaction of the films. Furthermore, the films presented hysteresis effects in the compression-decompression assay. The LB films were characterized by means of IRRAS spectroscopy, which indicated that the stearic acid is found to be in an orientation close to the substrate plane. UV-visible spectroscopic measurements showed little interaction between the chromophores. Lastly, the films were studied by cyclic voltammetry and showed a single electrochemical process attributed to the RuIII/II pair. Keywords: Ruthenium complex. 9-hidroxyphenalenone. Langmir-Blodgett films. Stearic acid

Methyl Ester Functionalized Phenalenyl Arene- and Bipyridine-Ruthenium-Based Complexes for Electroactive Langmuir-Blodgett Films

We report the synthesis of a new phenalenyl ligand, functionalized with a methyl ester electron withdrawing group, named 9-hydroxy-1-oxo-1H-phenalen-5-methyl carboxylate (L), and the generated complexes [Ru(bpy)2L]PF6 and [(η6-C6H6)Ru(L)Cl]. Compounds were characterized by spectroscopic and X-ray diffraction methods, and their electrochemical behavior was investigated via cyclic voltammetry and UV-vis spectroelectrochemistry. The one-electron oxidized compounds have an unpaired electron located in the phenalenyl ring, as supported by theoretical calculations (DFT) and EPR results. Langmuir-Blodgett (LB) films deposited by [Ru(bpy)2L]2+/3+ species mixed with stearic acid are electroactive, showing a quasi-reversible wave with E1/2Film1 = 0.74 V and E1/2Film2 = 0.81, which are promising systems that allow access to immobilized open-shell species in the film

Síntese e caracterização de complexos de rutênio com ligante derivado da 9-Hidroxifenalenona

Orientador: Dr. Herbert WinnischoferCoorientador: Eduard WestphalDissertação (mestrado) - Universidade Federal do Paraná, Setor de Ciências Exatas, Programa de Pós-Graduação em Química. Defesa : Curitiba, 27/09/2018Inclui referências: p. 117-127Resumo: No presente trabalho e apresentada a sintese e caracterizacao de um novo derivado da 9-hidroxifenalenona e a coordenacao desse ligante aos complexos derivados de ?6-arenorutenio(II) e 2,2'-bisbipiridinarutenio. O novo ligante 9??hidroxi?? 1??oxo??1H??fenalen??5??carboxilato de metila (L) foi sintetizado com sucesso e caracterizado por espectroscopias de RMN de 1H, 13C e HMBC, FTIR, UV-vis e espectrometria de massa, os quais confirmaram a pureza e a estrutura proposta. O ligante L tambem foi estudado por voltametria ciclica e por espectroeletroquimica UV-vis, na qual apresentou um processo eletroquimico reversivel. Os complexos [Ru(bpy)2L]PF6 e [(?6-C6H6)RuLCl] foram sintetizados a partir da reacao entre L e os respectivos precursores de rutenio. A caracterizacao estrutural dos complexos obtidos foi realizada por DRX de monocristal e espectroscopia de RMN de 1H. No caso do complexo [Ru(bpy)2L]PF6, foi tambem feita a espectrometria de massa de alta resolucao. Para auxiliar nos estudos espectroscopicos de UV-vis e FTIR, voltametria ciclica e espectroeletroquimica UV-vis, calculos teoricos de DFT foram realizados para a determinacao dos orbitais moleculares de L e de ambos os complexos. O complexo [Ru(bpy)2L]PF6 apresentou 4 processos eletroquimicos, sendo tres reversiveis e um irreversivel. Ja o complexo [(?6-C6H6)RuLCl] apresentou quatro processos eletroquimicos irreversiveis. Por fim o complexo [Ru(bpy)2L]PF6 foi utilizado na confeccao de filmes mistos de Langmuir e Langmuir-Blodgett com acido estearico. Os filmes [RuII(bpy)2L]-SA e [RuIII(bpy)2L]-SA apresentaram baixa area molecular indicando uma alta compactacao dos filmes. Alem disso, os filmes apresentaram efeito de histerese no ensaio de compressao-descompressao. Os filmes LB foram caracterizados por espectroscopia IRRAS, a qual indicou que o acido estearico se encontra em uma orientacao proxima ao plano do substrato. Medidas de espectroscopia UV-vis mostraram pouca interacao entre os cromoforos. Por fim, os filmes tambem foram estudados por voltametria ciclica e mostraram um processo eletroquimico reversivel atribuido ao par RuIII/II. Palavras-chave: Complexos de rutenio. 9-hidroxifenalenona. Filmes de Langmir- Blodgett. Acido estearico.Abstract: This work presents the synthesis and characterization of a new ligand derived from the 9-hydroxiphealenone molecule and its association with metal complexes derived from ?6-areneruthenium(II) and 2,2'-bisbipiridineruthenium. The new ligand named 9-hydroxi-1-oxo-1H-phenalen-5-methyl carboxialte (L) was successfully synthesized and characterized via 1H, 13C and HMBC NMR, FTIR, UVvisible spectroscopies and mass spectrometry, which confirmed its purity and structure. Cyclic voltammetry and UV-visible spectroelectrochemical studies were also performed with the ligand L, where a single reversible electrochemical process was observed. The complexes [Ru(bpy)2L]PF6 and [(?6-C6H6)RuLCl] were synthesized from the reaction between L and the metal precursors. The structural characterization of the obtained complexes was made by single crystal X-ray diffraction, as well as by 1H NMR spectroscopy. For the complex [Ru(bpy)2L]PF6, high resolution mass spectrometry was also made. In order to support the spectroscopy and electrochemistry studies, DFT calculations were performed to obtain the molecular orbitals of L and both ruthenium complexes obtained. The [Ru(bpy)2L]PF6 complex presented four electrochemical processes of which three are reversible and one irreversible. The [(?6-C6H6)RuLCl] complex showed four irreversible processes. Also, the [Ru(bpy)2L]PF6 complexes were used mixed with stearic acid in the confection of Langmuir and Langmuir-Blodgett films. The films [RuII(bpy)2L]-SA and [RuIII(bpy)2L]-SA presented low molecular area, indicative of a high compaction of the films. Furthermore, the films presented hysteresis effects in the compression-decompression assay. The LB films were characterized by means of IRRAS spectroscopy, which indicated that the stearic acid is found to be in an orientation close to the substrate plane. UV-visible spectroscopic measurements showed little interaction between the chromophores. Lastly, the films were studied by cyclic voltammetry and showed a single electrochemical process attributed to the RuIII/II pair. Keywords: Ruthenium complex. 9-hidroxyphenalenone. Langmir-Blodgett films. Stearic acid