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Doctoral Thesis
DOI
10.11606/T.75.2017.tde-30032017-094650
Document
Author
Full name
Vinicius Kalil Tomazett
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2016
Supervisor
Committee
Lima Neto, Benedito dos Santos (President)
Donatoni, Maria Carolina
Schwab, Ricardo Samuel
Deflon, Victor Marcelo
González, Eduardo René Pérez
Title in Portuguese
Síntese de monômeros luminescentes com norborneno e suas polimerizações via metátese
Keywords in Portuguese
bipiridina complexos
metalo-monômero
Metátese de olefinas
norborneno
ROMP
rutênio
tetra(pentafluorfenil)porfirina
Abstract in Portuguese

As reações de metatese assim como o desenvolvimento de complexos metal-carbeno (W, Mo, Ru) se tornaram amplamente conhecidos na química graças aos avanços que trouxeram. Na química orgânica, possibilitou a síntese de macrocíclos por meio da RCM e na química de polímeros a ROMP permitiu um alto grau de controle da polimerização além da alta reatividade dos catalisadores. Isso fez desta reação uma poderosa ferramenta no desenvolvimento de novos materias. A tentativa de combinar a processabilidade dos polímeros com as propriedades luminescentes de determinandos compostos tem sido tema de muitas pesquisas.O objetivo deste trabalho é derivatizar compostos luminescentes , como o complexo metálico [Ru(bpy)3] (PF6)2e a porfirina tetrakis-(pentafluorfenil)porfirina (TPPF20), com o monômero norborneno (NBE) para obtenção de monômeros lumiscentes passíveis de serem polimerizados via ROMP. Aqui será apresentado e discutido a síntese e a caracterização desses compostos partindo-se dos reagentes: ácido-5-norborneno-2carboxílico; etilenodiamina e o ácido-2,2'-bipiridina-4,4'-dicarboxílico, cis-[RuCl2(bpy)2] e a porfirina TPPF20. Os compostos foram sintetizados com rendimentos superiores a 60%, com exceção da obtenção da porfirina, e caracterizados por RMN - 1H e 13C; FTIR; UV-vis. Os estudos de copolimerização entre NEN (norborneno-etilenodiamina-norborneno), NBE-TPPF e [Ru(bpy)2(NBbpy)](PF6)2 foram feitos usando o catalisador de Grubbs segunda gereação. Os polímeros gerados foram caracterizados usando TG-FTIR e RMN-1H, as massas moleculares não puderam ser calculadas por GPC porém os estudos indicam obtenção de baixo peso molelcular. O material obtido foi testado como sensibilizador em vidro condutor ITO, porém não houve adsorção do composto necessitam algumas modificações no metalomonômero.

Title in English
Synthesis of luminescent norbornene monomers and their metathesis polymerization
Keywords in English
bipyridine complexes
metallo-monomer
norbornene
Olefin metathesis
ROMP
ruthenium
tetra(pentafluorophenyl)porphyrin
Abstract in English

The metathesis reactions as well as the development of metal-carbene complexes (W, Mo, Ru) became widely known in chemistry thanks to advancements brought. In organic chemistry, it enabled the synthesis of macrocycle by RCM. Useful for the synthesis of natural products. In polymer chemistry, ROMP, allow a high degree of polymerization control. This made the ROMP reaction a powerful tool in the development of new materials. In attempt to combine the processability of polymers with luminescent properties of such compounds has been the subject of several researchs. The aim of this work is to synthesize luminescent compounds based on [Ru(bpy)3] (PF6)2 metal complex and on the porphyrin tetrakis-(pentafluorphenyl)porphyrin (TPPF20), funcionalized with pendant norbornene monomer (NBE) to obtain lumiscentes monomers which can undergo ROMP polymerization. Here will be discussed the synthesis and characterization of these compounds using as starting materials: 5-norbornene-2-carboxylic acid; ethylenediamine; 2,2'-bipyridine-4,4'dicarboxylic acid, cis-[RuCl2(bpy)2] and the porphyrin TPPF20. The compounds were synthesized with yields higher than 60%, with the exception of the porphyrin, and characterized by 1H and 13C-NMR; FTIR; UV-vis. Copolymerization reaction between NEN (Norbornene-Ethylenediamine-Norbornene), NBE-TPPFe [Ru(bpy)2(NBbpy)] (PF6)2 were performed using Grubbs second generation catalyst. Resultinf polymers were characterized by TG-FTIR and 1H-NMR, molecular weight could not be measured by GPC, since polymers were insoluble, but studies indicate low molelcular weight. The material obtained was tested as sensitizer in conductive glass ITO. The polymer didn't adsorb in to the ITO surface. Some changes in the compound molecular structure are required to improve adsorption.

 
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Publishing Date
2017-03-30
 
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