Insight into the roles of structures and energy levels of mono- and bis-β-diketones on sensitizing Nd(iii) NIR-luminescence

Abstract

Three neodymium complexes Nd(TTA)₃(DMSO)₂ (1, TTA = 2-thenoyltrifluoroacetone), Nd₂(BDT)₃(DMSO)₆ (2, BDT = bis(4,4,4-trifluoro-1,3-dioxobutyl)thiophene) and Nd₂(BTT)₃(DMSO)₄ (3, BTT = bis(4,4,4-trifluoro-1,3-dioxobutyl)(2,2′-bithiophene)) constructed from three thiophene-based β-diketonate ligands, were prepared for the purpose of building the relationships between the structures, energy levels of the complexes and NIR luminescence properties of Nd(III) ions. X-ray crystallographical analysis reveals that complex 1 is a mononuclear structure, the central Nd(III) ion is coordinated by eight oxygen atoms from three mono-β-diketones (TTA) and two DMSO, whereas, complexes 2 and 3 adopt triple-stranded dinuclear structures, in which the two Nd(III) ions are wrapped by three bis-β-diketones, the central Nd(III) ions are nine and eight coordinated by oxygen atoms from ligands and the coordinated DMSO molecules. The photophysical properties related to the electronic transition are characterized by the absorbance spectra, the excitation spectra, the phosphorescence spectra, the emission spectra, the emission quantum yields, and the emission lifetimes. The luminescence quantum yields experiment reveals that the dinuclear complexes (0.49% and 0.33% for 2 and 3) show higher luminescence efficiencies compared to the mononuclear complex 1 (0.22%). This enhancement is mainly attributed to their binuclear structures, which effectively represses the nonradiative transition caused by high-energy oscillators in ligands and/or solvents. On the other hand, the energy level matching also plays an important role in this enhancement.