Influence of structural changes on photophysical properties of terpyridine derivates: Experimental studies and theoretical calculations

D. Toledo (1) , F. Brovelli (2) , J. Soto-Delgado (3) , O. Peña (4) , J.-Y. Pivan (4) , Y. Moreno (3)

1 Departamento de Química Analítica e Inorgánica
2 Universidad de Concepción - University of Concepcion [Chile]
3 UNAB - Universidad Andrés Bello [Santiago]
4 ISCR - Institut des Sciences Chimiques de Rennes

Four terpyridine ligands containing different aryl substituents 4'-(4-quinolinyl)-3,2':6′,3″-terpyridine (3-qtpy), 4'-(4-quinolinyl)-2,2':6′,2″-terpyridine (2-qtpy), 4'-(3-methyl-2-thienyl)-4,2':6′,4″-terpyridine (4-stpy) and 4'-(3-methyl-2-thienyl)-2,2':6′,2″-terpyridine (2-stpy) were synthesized in a one-pot procedure and characterized by elemental analysis, FT-IR and 1H- and 13C NMR spectroscopy. Additionally, the 2-stpy structure was confirmed by single crystal X-ray diffraction analysis. The influence of the N-position in the tpy and aryl substituents on the photophysical properties was systematically investigated by spectroscopic methods and simulated by density functional theory (DFT and TD-DFT) calculations. Thermal stability was observed until about 280 °C, making these kind of ligands interesting candidates for their use as complex ligands, which are obtained by solvothermal synthesis under temperatures of about 180 °C. The electrochemical behavior was also investigated. All molecules show irreversible anodic and cathodic voltammetric peaks in organic medium.

Mots clés: Density functional theory; Chelation; Ligands; Nuclear magnetic resonance spectroscopy; Single crystals; Spectroscopic analysis; Substitution reactions; X ray diffraction analysis; 13C NMR spectroscopy; Electrochemical behaviors; One-pot procedures; Photophysical properties; Single crystal X-ray diffraction analysis; Theoretical calculations; Spectroscopic method; Crystal structure; Solvothermal synthesis

Domaines: Chimie organique; Chimie théorique et/ou physique

D. Toledo, F. Brovelli, J. Soto-Delgado, O. Peña, J.-Y. Pivan, et al.. Influence of structural changes on photophysical properties of terpyridine derivates: Experimental studies and theoretical calculations. Journal of Molecular Structure, 2018, 1153, pp.282-291. ⟨10.1016/j.molstruc.2017.10.011⟩. ⟨hal-01639696⟩