Effect of the aromatic substituent on the para-position of pyridine-bis(oxazoline) sensitizers on the emission efficiency of their EuIII and TbIII complexes

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 49; no. 48; pp. 17699 - 17708
• Main Authors: Ana de Bettencourt-Dias, Rossini, Jeffrey S K, Sobrinho, Josiane A
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 22.12.2020
• Subjects: Atomic energy levels; Crystallography; Dichloromethane; Emission; Energy transfer; Excitation; Parameters
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d0dt03135f

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, β = 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, β = 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=Eu and 24.0% for Ln=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 with cell parameters a = 9.1845(2) Å, b = 10.3327(2) Å, c = 11.9654(2) Å, α = 98.419(1)°, β = 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)°, β = 86.355(1)°, γ = 77.223(1)°, V = 1231.95(3) Å3, respectively.