Stark Sublevel-Based Thermometry with Tb(III) and Dy(III) Complexes Cosensitized via the 2-Amidinopyridine Ligand.
Stark Sublevel-Based Thermometry with Tb(III) and Dy(III) Complexes Cosensitized via the 2-Amidinopyridine Ligand.
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DOI：
10.1021/acs.inorgchem.0c01534
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发表时间：
2020-07
影响因子：
4.6
通讯作者：
Alexandros A. Kitos;D. Gálico;R. Castañeda;Jeffrey S. Ovens;M. Murugesu;Jaclyn L. Brusso
中科院分区：
文献类型：
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作者：
Alexandros A. Kitos;D. Gálico;R. Castañeda;Jeffrey S. Ovens;M. Murugesu;Jaclyn L. Brusso
我们采用了基于酰胺的配位体骨架来分离一系列的单核稀土配合物。所用的N-2-吡啶亚胺-2-吡啶酰胺(PY2ImAm)经过金属辅助的水解得到配体2-氨基吡啶(PYAm)，它与生成[Ln(Acac)3(PYAm)]的稀土离子配位，其中Ln=Eu(III)(1)，Gd(III)(2)，Tb(III)(3)，Dy(III)(4)以及Y(III)类似物(5)。Eu(III)、Tb(III)和Dy(III)同系物分别表现出红光、绿光和黄光的特征发射，发射量子产率分别为3%、65%和8%。由于Stark子能级热布居数的变化，Tb(III)和Dy(III)配合物可以作为有效的光学温度计，对3和4的最大相对灵敏度分别为1.57%K-1和2.03%K-1。这些结果证明了PYAM作为敏化稀土离子的天线的可行性。
Amidine-based ligand frameworks were employed to isolate a series of mononuclear lanthanide complexes. The employed N-2-pyridylimidoyl-2-pyridylamidine (Py2ImAm) undergoes metal-assisted hydrolysis yielding the ligand 2-amidinopyridine (PyAm), which coordinates to the lanthanide ions affording [Ln(acac)3(PyAm)], where Ln = Eu(III) (1), Gd(III) (2), Tb(III) (3), Dy(III) (4) along with the Y(III) analogue (5). The Eu(III), Tb(III), and Dy(III) congeners exhibit characteristic emissions of red, green, and yellow light, respectively, with emission quantum yields of 3, 65, and 8%, respectively. Due to changes in the thermal population of the Stark sublevels, the Tb(III) and Dy(III) complexes can be used as efficient optical thermometers with maximum relative sensitivities of 1.57 and 2.03% K-1 for 3 and 4, respectively. These results demonstrate the viability of PyAm as an antenna for the sensitization of lanthanide ions.