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Reactivity of the trinuclear cluster [Ru3O(CH3COO)6(CH3OH)3]CH3COO: use as a precursor of a series of new binuclear ¼-oxo complexes with phenanthrolines

Grant number: 21/14279-3
Support Opportunities:Scholarships in Brazil - Doctorate (Direct)
Effective date (Start): August 01, 2022
Effective date (End): February 28, 2027
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
Principal Investigator:Sofia Nikolaou
Grantee:Nicolle Azevedo Portela dos Santos
Host Institution: Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto (FFCLRP). Universidade de São Paulo (USP). Ribeirão Preto , SP, Brazil


This project aims to study the reactivity of the trinuclear cluster [Ru3O(CH3COO)6(CH3OH)3]CH3COO against the orthometallation reaction of ligands from the phenanthroline family. Therefore, the project aims to synthesize, from this cluster, four novel binuclear ¼-oxo ruthenium complexes with the general formula [Ru2(¼-O){·2(N,N)-phen}2{¼-·1(C ),·2(N,N)-phen}2](CH3COO)2, phen= 1,10-phenanthroline (1), 5-chloro-1,10-phenanthroline (2), 5-methyl-1.10 -phenanthroline (3) and 1,10-phenanthroline-5,6-dione (4), in addition to performing a kinetic study of the orthometallation reaction. The choice of ligands is based on the properties of the phenanthroline ligand (bidentate, planar, and hydrophobic), on the presence of potentially interesting substituents for biological interactions and properties, and also on the possibility of extending the structure of the 1,10-phenanthroline-5,6-dione ligand, based on its reaction with aromatic diamines and potential to obtain phenazines. The characterization of the complexes will be done through elemental analysis, cyclic voltammetry, electronic absorption spectra in the UV-Vis region and vibrational in the infrared and NMR region. Other complementary techniques, such as mass spectrometry and differential pulse voltammetry can be used if necessary. Interaction studies of the complexes with fs-DNA (salmon sperm DNA) and HSA (human serum albumin) will be carried out in order to infer, at first from chemical experiments, the potential of the complexes for application as metal-based drugs. These experiments will be carried out by spectrophotometric titrations and application of the Stern-Volmer treatment. In both cases (interaction with DNA and HSA), circular dichroism experiments can be performed in a complementary way. The intention is to carry out the photophysical characterization of the complexes staged abroad, through measurements in steady-state and time-resolved in a fast decay regime on a femtosecond scale. (AU)

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