Deciphering intersystem crossing and energy transfer mechanisms in a nonacoordinated ternary europium(iii) complex: a combined spectroscopic and theoretical study

RSC Adv. 2024 Oct 15;14(44):32573-32582. doi: 10.1039/d4ra06727d. eCollection 2024 Oct 9.

Abstract

A monochromatic red emitting nonacoordinate organoeuropium complex with the formula [Eu(hfaa)3(Ph-TerPyr)] (Eu-1) incorporating hexafluoroacetylacetone (hfaa) primary ligands and a tridentate 4'-phenyl-2,2':6',2''-terpyridine (Ph-TerPyr) ancillary ligand has been synthesized. The complex was characterized by analytical and spectroscopic methods, and its structure was established by single crystal X-ray diffraction (SC-XRD) analysis at low temperature, which explicitly confirms that the coordination sphere is composed of a EuO6N3 core. Under the UV excitation, Eu-1 displayed typical red emission in solution with a long-excited state lifetime (τ obs = 1048.06 ± 9.39 μs) with a good photoluminescence quantum yield (Q L Eu = 41.14%). We have utilized pump-probe ultrafast transient absorption spectroscopy in tandem with the time-dependent density functional theory (TD-DFT) and the Lanthanide Luminescence Software Package (LUMPAC) to explore the intricate photophysical event that occurs in the vicinity of the ligands of Eu-1 sensitized photoluminescence (PL).