A new spectroscopic system for direct photoluminescence of lanthanide ions (Ln(III)) through electronic transitions within the 4fn manifold is described. The system is based on an injection seeded frequency tripled (λ = 355 nm) Nd:YAG pump laser coupled with a master
oscillator power oscillator (MOPO). The MOPO delivers an average pulse energy of ∼60 mJ/pulse, is continuously tunable from 425 to 690 nm (Signal) and 735 to 1800 nm (Idler) with a linewidth of <0.2 cm−1, and has a pulse duration of 10–12 ns. Aqueous solutions
containing two polyaminocarboxylate complexes, ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), and Ln3+ aqua ion for several lanthanides including Eu(III), Tb(III), Dy(III), and Sm(III)) are used as steady-state and time-resolved photoluminescence
standards. The versatility of the instrument is demonstrated by excitation scans over a broad visible range for aqueous solutions of complexes of Eu(III), Dy(III), Sm(III), and Tb(III). The Eu(III) excitation band (7Fo→5Do) is recorded over
a range of complex concentrations that are 1000–fold less than reported previously, including Eu(EDTA) (1.00 nM), Eu(DTPA) (1.00 nM), and Eu(III) aqua ion (50.0 nM). Emission spectra are recorded in the visible range for Ln(III) complexes at pH 6.5 and 1.00 mM. Excited-state lifetimes
for the standards were constant as a function of concentration from 10.0 nM to 1.00 mM for Eu(EDTA) and Eu(DTPA) and from 100 nM to 1.00 mM for Eu(III) aqua ion. Photoluminescence lifetimes in H2O and D2O are recorded and used to calculate the number of bound water molecules
for all complexes.
Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260-3000
Publication date: May 1, 2009
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