RESUMO
Two efficient lanthanide ion sensitizers 2,6-bis(oxazoline)-4-phenyl-pyridine (PyboxPh, 1) and 2,6-bis(oxazoline)-4-thiophen-2-yl-pyridine (Pybox2Th, 2) were synthesized. 1 crystallizes in the monoclinic space group P21/c with cell parameters a = 16.3794(4) Å, b = 7.2856(2) Å, c = 11.7073(3) Å, ß = 97.229(1)° and V = 1385.97(6) Å3. 2 crystallizes in the monoclinic space group P21/n with cell parameters a = 5.9472(2), b = 16.0747(6), c = 14.3716(5) Å, ß = 93.503(1)° and V = 1371.35(8) Å3. Photophysical characterization of 1 shows that its triplet state energy is located at 22 250 cm-1 and efficient energy transfer is observed for EuIII and TbIII. Solutions of [Ln(PyboxPh)3]3+ in dichloromethane display an emission efficiency of 37.2% for Ln[double bond, length as m-dash]Eu and 24.0% for Ln[double bond, length as m-dash]Tb. The excited state lifetimes for EuIII and TbIII are 2.227 ms and 723 µs, respectively. The triplet state energy of 2 is located at 19 280 cm-1 and is therefore too low to efficiently sensitize TbIII emission. However, the sensitization of EuIII is effective, with an emission quantum yield of 14.5% and an excited state lifetime of 714 µs. This shows that the derivatization of the chelator is strongly influenced by the aromatic substituents on the para-position of the pyridine ring. New isostructural 1 : 1 complexes of PyboxPh with EuIII (3) and TbIII (4) were also isolated and crystallize in the triclinic space group P1[combining macron] with cell parameters a = 9.1845(2) Å, b = 10.3327(2) Å, c = 11.9654(2) Å, α = 98.419(1)°, ß = 108.109(1)°, γ = 91.791(1)°, V = 1064.08(4) Å3 and a = 7.8052(1) Å, b = 11.8910(1) Å, c = 14.2668(2) Å, α = 72.557(1)°, ß = 86.355(1)°, γ = 77.223(1)°, V = 1231.95(3) Å3, respectively.
RESUMO
The isolation of emissive materials with lanthanide ions is a topic of interest for imaging, display, and sensing applications, and it requires tuning of the electronics of the systems, such that, during the process of sensitization of the metal-centered luminescence, energy transfer from the sensitizer to the lanthanide ion is efficient and the resulting materials have the characteristics required for a given application. We discuss here our group's work in controlling the singlet- and triplet-state energies of sensitizing ligands through the choice of functional groups on the pyridine rings chelating to the lanthanide ions and show how we achieved progressively higher emission efficiencies. We describe targeted functionalization that led to highly emissive systems in solution and in the solid state and to new metallopolymers with norbornene or dicyclopentadiene-based backbones and pyridinebis(oxazoline) pendants, which display red EuIII-based, green TbIII-based, and, for the first time, blue TmIII-based emission.
