Hetero/homogeneous carbon dioxide photocatalysis by mono and polynuclear ReI compounds containing modified naphthalimides

• Grant number: 25/12441-9
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)
• Start date: January 01, 2026
• End date: December 31, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
• Principal Investigator: Sofia Nikolaou
• Grantee: Luis Guilherme Alves do Nascimento
• Supervisor: Osamu Ishitani
• Host Institution: Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto (FFCLRP). Universidade de São Paulo (USP). Ribeirão Preto , SP, Brazil
• Institution abroad: Hiroshima University, Japan
• Associated to the scholarship: 22/16402-0 - Synthesis, characterization and investigation of photoinduced properties of Re(I) tricarbonyls compounds coordinated with polypyridine and naphthalimidic ligands, BP.DD

Abstract

This project aims to investigate the intra- and intermolecular photoinduced electron transfer processes that are associated with the solar to chemical energy conversion by mononuclear ReI complexes, which are being evaluated in the main research project (FAPESP process number 2022/16402-0), of general formula fac-[Re(CO)3(phen)(py-NI-R)]PF6, where phen = 1,10-phenantroline, py-NI-R = N-pyridyl-1,8-naphthalimide if R = H (1); 4-bromo-N-pyridyl-1,8-naphthalimide if R = Br (2); or 4-amino-N-pyridyl-1,8-naphthalimide if R = NH2 (3). In addition, the synthesizes, characterization (by absorption and emission UV-visible, infrared and NMR spectroscopies; cyclic voltammetry, mass spectrometry, and elemental analysis), and study of heterogenous photocatalytic behavior of two novel ReI-RuII hybrid photocatalysis of general formula [Ru(Me2-bpy)((H2PO3CH2)2-bpy)(phen-NDI)Re(CO)3Cl](PF6)2 (4), [Ru((H2PO3CH2)2-bpy)(phen-NDI)2Re(CO)3Cl](PF6)2 (5), where Me2-bpy = 4,4¿-dimethyl-2,2¿-bipyridine, (H2PO3CH2)2-bpy = 4,4¿-bis(dimethylphosphonate)-2,2¿-bipyridine, phen-NDI = N,N'-di(1,10-phenanthroline)-1,4,5,8-naphthalene diimide is proposed. The interest in this research rises in the same direction as the Sustainable Development Goals 12 and 13, trying to solve the problem of carbon dioxide (CO2) high atmospheric concentrations. Recent artificial photosynthesis literature from both our and Professor Ishitani's research groups showed that ReI mono and polinuclear complexes can powerfully photoreduce the CO2 in more value-added products, using chemical green reagents, by photoinduced electro transfer reactions in homo and heterogenous catalysis. Furthermore, we recently contributed to the naphthalimide literature, including the attached PhD project, showing its importance in supramolecular devices and photoinduced electron (or energy) transfer. Therefore, the combination of the naphthalimide chemistry with the ReI-RuII hybrid photocatalysis knowledge will supply mutual interest to our laboratories and Professor Ishitani's group, observing how the naphthalimide can impact the photosensitizer and photocatalyst electronic structure under wide conditions. (AU)