Predicting Efficient Antenna Ligands for Tb(III) Emission
Predicting Efficient Antenna Ligands for Tb(III) Emission
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DOI：
10.1021/ic801904s
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发表时间：
2009-01-19
影响因子：
4.6
通讯作者：
Raymond, Kenneth N.
中科院分区：
文献类型：
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作者：
Samuel, Amanda P. S.;Xu, Jide;Raymond, Kenneth N.
合成了一系列对位取代的2-羟基邻苯二甲酰胺配体（5LI-IAM-X）（X = H，CH_3，（C=O）NHCH_3，SO_3-，NO_2，OCH_3，F，Cl，Br）的Tb（III）配合物，研究了邻苯二甲酰胺环上取代对配体和Tb（III）发光的影响，建立了预测发色团修饰对Tb（III）发光影响的方法。配体的单重态和三重态的激发态的能量被发现线性增加的取代基的; C-撤回能力。实验结果得到了时间依赖性密度泛函理论计算模型系统，预测配体的单线态和三线态的能量在类似的实验值的5%。Tb（III）配合物的量子产率（Phi）值随着配体的三重态能量而增加，这部分是由于三重态的热再布居引起的非辐射失活减少。总之，实验和理论结果作为一个预测工具，可以指导用于敏化镧系发光的配体的合成。
A series of highly luminescent Tb(III) complexes of para-substituted 2-hydroxyisophthalamide ligands (5LI-IAM-X)has been prepared (X = H, CH3, (C=O)NHCH3, SO3-, NO2, OCH3, F, Cl, Br) to probe the effect of substituting the isophthalamide ring on ligand and Tb(III) emission in order to establish a method for predicting the effects of chromophore modification on Tb(III) luminescence. The energies of the ligand singlet and triplet excited states are found to increase linearly with the;c-withdrawing ability of the substituent. The experimental results are supported) by time-dependent density functional theory calculations performed on model systems, which predict ligand singlet and triplet energies within similar to 5% of the experimental values. The quantum yield (Phi) values of the Tb(III) complexes increase with the triplet energy of the ligand, which is in part due to decreased non-radiative deactivation caused by by thermal repopulation of the triplet. Together, the experimental and theoretical results serve as a predictive tool that can guide the synthesis of ligands used to sensitize lanthanide luminescence.