Abstract
Herein, we describe the preparation, characterization and photophysical properties of neutral lanthanide complexes containing a redox-active ligand 1-(2-pyridylazo)-2-phenanthrol (papl). The complexes likely share similar structural features and bear the formulation Ln(papl)3 (Ln(III) = Gd, Dy, Tb), which is supported by electrospray ionization mass spectrometry, CHN analysis, FT-IR and UV–Vis spectroscopy. The synthesis and structural properties of a related complex, Ho(qapl)3 (where qapl = 10-(8-quinolylazo)-9-phenanthrol), is also reported. The complexes feature ligand-centered redox activity, similar to other reported transition metal complexes with papl. Variable temperature magnetic susceptibility measurements (DC and AC) suggest typical free-ion magnetism without any slow-relaxation dynamics. The photophysical properties of the ligand and complexes were investigated and the results of emission spectroscopy indicate ligand-centered processes.
Highlights
Lanthanide ion complexes are of interest for the production of luminescent and magnetic materials, including as diagnostic agents in magnetic resonance imaging (MRI) [1,2,3], biosensors [4,5], and single molecule magnets (SMMs and single ion magnets (SIMs), respectively) [6,7]
Three equivalents of the deprotonated ligand bind to the metal ion to produce nine coordinate species with a likely tricapped trigonal prismatic geometry at the lanthanide ion, analogous to the Ho(qapl)3 complex reported in this work
We investigated the luminescent properties of 1–3 and the uncoordinated papl ligand since there are very few reports of the emission properties of lanthanide complexes coordinated to arylazo ligands
Summary
Lanthanide ion complexes are of interest for the production of luminescent and magnetic materials, including as diagnostic agents in magnetic resonance imaging (MRI) [1,2,3], biosensors [4,5], and single molecule (or ion) magnets (SMMs and SIMs, respectively) [6,7]. The observed luminescence in these complexes is the result of transitions within the energy level manifold of the lanthanide ion and this generally results in the characteristic sharp emission spectra observed for these complexes. Another result of the isolation of the f -orbitals from the ligand field is that lanthanide ion complexes often exhibit unique. Inorganics 2018, 6, x FOR PEER REVIEW magnetic properties generally easy to interpret as free ion magnetism by consideration of the total of the total angular momentum in of thethe form theterm free ion term symbol. Depending on the angular momentum of the ion of in the the ion form freeofion symbol.
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