Azido- and amino-substituted dipicolinates for the sensitization of the luminescent lanthanides EuIII and TbIII
Azido- and amino-substituted dipicolinates for the sensitization of the luminescent lanthanides EuIII and TbIII
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DOI：
10.1016/j.ica.2020.120003
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发表时间：
2021
影响因子：
2.8
通讯作者：
Katherine R. Johnson;Ana de Bettencourt-Dias
中科院分区：
文献类型：
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作者：
Katherine R. Johnson;Ana de Bettencourt-Dias
合成并表征了叠氮基或氨基取代的双甲酸酯类配体。得到了EN3、CN3、CNH2和ENH2的晶体结构，并研究了它们对LnIII发光(LnIII=EuIII和TbIII)的敏化能力。[Ln(CN_3)_3]_3+、[Ln(CN_3)_3]_3+、[Ln(CN_2)_3]_3+的发光效率分别为ϕEu=0.11%、0.15%和13.8%；[Ln(CN_3)_3]_3+、[Ln(En_3)_3]_3+、[Ln(En_2)_3]_3+的ϕ_b分别为0.30%、0.27%和28.9%。最高的发光效率为：[Eu(EnH2)3]3+的ϕEu=114.4%，[Tb(NH2)3]3+的ϕTb=529.7%。所有配体都观察到了相似的1S和3T激发态能量，并不能解释观察到的TbⅢ和EuⅢ配合物发光效率的差异。进一步的分析表明，叠氮类化合物不具有光稳定性，这可能是导致发光效率较低的原因之一。
Dipicolinate-based ligands substituted with azido- or amino- functional groups were synthesized and characterized. Crystal structures ofEN3, CN3, CNH2,andENH2were obtained, and the ability of these compounds to sensitize LnIIIluminescence (LnIII= EuIIIand TbIII) was explored. Luminescence efficiencies of EuIIIand TbIIIwere determined and are ϕEu= 0.11%, 0.15%, and 13.8% for [Ln(CN3)3]3+, [Ln(EN3)3]3+, [Ln(CNH2)3]3+, respectively, and ϕTb= 0.30%, 0.27%, and 28.9% for [Ln(CN3)3]3+, [Ln(EN3)3]3+, [Ln(ENH2)3]3+. The highest luminescence efficiencies are ϕEu= 14.4% for [Eu(ENH2)3]3+and ϕTb= 29.7% for [Tb(CNH2)3]3+. Similar1S and3T excited state energies were observed for all ligands and did not explain the observed discrepancies in luminescence efficiency of their TbIIIand EuIIIcomplexes. Further analysis revealed that the azido-derivatives were not photostable, which likely contributed to the low luminescence efficiency.