Photoluminescence and magnetic properties of isostructural europium(III), gadolinium(III) and terbium(III) oxamate-based coordination polymers.

Developing and investigating advanced multifunctional materials with magnetic properties as candidates for assembling spin qubits for quantum computing is imperative. A new polytopic ligand based on oxamate and aniline was used to promote the synthesis of three neutral homometallic lanthanide-coordinated polymers. New complexes with the formula {Ln(phox)3(DMSO)2(H2O)}n, where Ln = Eu3+ (1), Gd3+ (2), and Tb3+ (3) [phox = N-(phenyl)oxamate and DMSO = dimethylsulfoxide], were synthesized and well characterized by spectroscopic methods as well as X-ray crystallographic analysis. All crystalline structures comprise neutral zigzag chains. The lanthanide ions are linked by three phox ligands, in which two oxygen atoms from two different ligands are responsible for connecting the trivalent lanthanide ions, and one phox ligand completes the coordination sphere in a bis-bidentate mode, together with two DMSO molecules and one water coordination molecule. The coordination sphere of lanthanide ions consisted of spherical capped square antiprism (CSAPR-9) symmetry. The magnetic properties of 1-3 were investigated in the 2-300 K temperature range. The dynamic (ac) magnetic properties of 2 reveal a frequency dependence involving the phonon bottleneck mechanism below 33 K under nonzero applied dc magnetic fields, resulting in an example of a field-induced single-molecule magnet. Solid-state photophysical measurements for Eu3+ (1) and Tb3+ (3) complexes indicate that the N-(phenyl)oxamate ligands are very efficient in sensitizing the lanthanide(III) ions in the visible region of the electromagnetic spectrum. Compounds 1 and 3 exhibited an emission in the red and green regions, respectively. Experimental results and theoretical calculations using the Sparkle/RM1 method support a quantum efficiency of ∼72% for 1, suggesting its potential as a candidate for light conversion molecular devices (LCMDs).

Luminescent Supramolecular Metallogels: Drug Loading and Eu(III) as Structural Probe.

Supramolecular metallogels combine the rheological properties of gels with the color, magnetism, and other properties of metal ions. Lanthanide ions such as Eu(III) can be valuable components of metallogels due to their fascinating luminescence. In this work, we combine Eu(III) and iminodiacetic acid (IDA) into luminescent hydrogels. We investigate the tailoring of the rheological properties of these gels by changes in their metal:ligand ratio. Further, we use the highly sensitive Eu(III) luminescence to obtain information about the chemical structure of the materials. In special, we take advantage of computational calculations to employ an indirect method for structural elucidation, in which the simulated luminescent properties of candidate structures are matched to the experimental data. With this strategy, we can propose molecular structures for different EuIDA gels. We also explore the usage of these gels for the loading of bioactive molecules such as OXA, observing that its aldose reductase activity remains present in the gel. We envision that the findings from this work could inspire the development of luminescent hydrogels with tunable rheology for applications such as 3D printing and imaging-guided drug delivery platforms. Finally, Eu(III) emission-based structural elucidation could be a powerful tool in the characterization of advanced materials.