Diarylphosphate as a New Route for Design of Highly Luminescent Ln Complexes

Organophosphate-chloride complexes [{(2,6-Pr₂C₆H₃-O)₂POO}₂LnCl(CH₃OH)₄]·2CH₃OH, Ln = Nd (1), Eu (2), Gd (3), and Tb (4) have been obtained and structurally characterized. Their reaction with 2,2':6',2″-terpyridine leads to the formation of 1:1 adducts ([{(2,6-Pr₂C₆H₃-O)₂POO}₂LnCl(terpy)(H₂O)₂(CH₃OH)], Ln = Eu (5), Gd (6), Tb (7) with exception of Nd, where tris-diisopropylphenylphosphate complex [{(2,6-Pr₂C₆H₃-O)₂POO}₃Nd) (terpy)(H₂O)(CH₃OH)] (8) was obtained due to the ligand metathesis. A bright luminescence observed for the Eu and Tb organophosphate complexes is the first example of an application of organophosphate ligands for 4f-ions luminescence sensitization. Photophysical properties of all complexes were analyzed by optical spectroscopy and an energy transfer scheme was discussed. A combination of two types of ligands into the coordination sphere (phosphate and phenanthroline) allows designing the Eu surrounding with very high intrinsic quantum yield QEuEu (0.92) and highly luminescent Ln complexes for both visible and near-infrared (NIR) regions.