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Synthesis of Functionalized Metal-monomers of Barrelene with Polipyridines of Ru(II) to Obtaining Polymeric Sensitizers via ROMP

Grant number: 12/24617-4
Support Opportunities:Scholarships in Brazil - Doctorate
Effective date (Start): April 01, 2013
Effective date (End): September 30, 2016
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
Principal Investigator:Benedito dos Santos Lima Neto
Grantee:Vinícius Kalil Tomazett
Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil


In this work is proposed the synthesis of ruthenium bipyridine-based metalopolymers from barrelene units, which will be synthesized in four steps. Once synthesized the barrelene, it will be functionalized with phenanthrene to increase the absorption of light with its conjugate chain, besides the bipyridine, that is able to coordinate to the metal ruthenium and to produce a photoactive complex and embed it in the polymer side chain.The ruthenium metal center will be coordinated with other ancillary ligands, as the acid 4.4'-dicarboxylic-2.2'-bipyridine (H2dcbpy) and the thiocyanete (NCS) to modulate their photochemical properties.Once obtained the metallomonomer, it will undergo ROMP with catalysts already developed by the group to obtain poly(p-phenyleno-vinylidene) (PPV), with side chains composed by both photoactive complex and phenanthrene.The photochemical and photophysical properties of the metallopolymer will be studied through theoretical calculations made by DFT and TD-DFT and compared to studies of light absorption, photoluminescence, cyclic-voltammetry, etc.

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Scientific publications
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
TOMAZETT, VINICIUS K.; SANTOS, WILLY G.; LIMA-NETO, BENEDITO S.. Infrared spectroscopy as an effective tool in ring-opening metathesis polymerization: monitoring the polymerization kinetics of norbornene with amine-based Ru catalysts in real time. Reaction Kinetics Mechanisms and Catalysis, v. 120, n. 2, p. 663-672, . (12/19823-4, 15/13756-1, 12/24617-4)
Academic Publications
(References retrieved automatically from State of São Paulo Research Institutions)
TOMAZETT, Vinícius Kalil. Synthesis of luminescent norbornene monomers and their metathesis polymerization. 2016. Doctoral Thesis - Universidade de São Paulo (USP). Instituto de Química de São Carlos (IQSC/BT) São Carlos.

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