Lanthanide Luminescence and Thermochromic Emission from Soft-Atom Donor Dichalcogenoimidodiphosphinate Ligands
Lanthanide Luminescence and Thermochromic Emission from Soft-Atom Donor Dichalcogenoimidodiphosphinate Ligands
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软原子供体二硫族亚胺二膦酸盐配体的镧系元素发光和热致变色发射
DOI：
10.1021/acs.inorgchem.2c02260
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发表时间：
2022
影响因子：
4.6
通讯作者：
Stoll, Sarah L.
中科院分区：
文献类型：
--
作者：
Stewart, Orlando C.;Marwitz, Alexander C.;Swanson, Joel;Bertke, Jeffery A.;Hartman, Tyler;Monteiro, Jorge H.;de Bettencourt-Dias, Ana;Knope, Karah E.;Stoll, Sarah L.
研究了Eu[N（SPPh 2）2]2（THF）2（1）和Eu[N（SePPh 2）2]2（THF）2（2）两种二价铕配合物的发光性质。第一个配合物Eu[N（SPPh 2）2]2（THF）2（1）与文献报道的配合物2结构同晶，在室温下发光，冷却后有热致变色发光。发现配合物Eu[N（SePPh 2）2]2（THF）2（2）也具有热致变色性质，但发光强度对温度敏感。室温和低温（100 K）单晶X射线结构研究表明1和2的金属配位的几何畸变，这对于理解这些配合物的热致变色行为可能是重要的.配体为1的三价铕配合物Eu[N（SPPh 2）2]3（3）的结构也与温度有关，其发光强度与温度有关，在室温下没有可观察到的发光，但在77 K下有很强的发光。采用变温拉曼光谱法测定了Eu[N（SPPh 2）2]3（3）的发光起始温度，其中615 nm（5D 0 → 7 F2跃迁）峰在130 K以上被猝灭。的紫外-可见漫反射率的3提供了一个LMCT带的证据，支持热激活的LMCT猝灭Eu（III）的发射状态的机制。合成了一系列Ln[N（SPPh 2）2]3（Ln = Eu（3）Pr（4），Nd（5），Sm（6），Gd（7），Tb（8））和Ln[N（SePPh 2）2]3（Ln = Pr（9），Nd（10，结构已报道），Sm（11），Gd（12），Q = Se）的同晶三价镧系配合物，并对其结构进行了表征。Ln = Pr、Nd、Sm和Tb的配合物具有室温发光。这项研究提供了温度依赖性发光的Eu 2+和Eu 3+，和使用软原子供体配体敏化镧系元素发光的范围内的三价镧系元素，跨越近红外和可见光发射器的例子。
The luminescence properties of two divalent europium complexes of the type Eu[N(SPPh2)2]2(THF)2(1) and Eu[N(SePPh2)2]2(THF)2(2) were investigated. The first complex, Eu[N(SPPh2)2]2(THF)2(1), was found to be isomorphous with the reported structure of complex2and exhibited room temperature luminescence with thermochromic emission upon cooling. We found the complex Eu[N(SePPh2)2]2(THF)2(2) was also thermochromic but the emission intensity was sensitive to temperature. Both room temperature and low temperature (100 K) single crystal X-ray structural investigation of1and2indicate geometric distortions of the metal coordination, which may be important for understanding the thermochromic behavior of these complexes. The trivalent europium complex Eu[N(SPPh2)2]3(3) with the same ligand as1was also structurally characterized as a function of temperature and exhibited temperature-dependent luminescence intensity, with no observable emission at room temperature but intense luminescence at 77 K. Variable temperature Raman spectroscopy was used to determine the onset temperature of luminescence of Eu[N(SPPh2)2]3(3), where the 615 nm (5D0→7F2transition) peak was quenched above 130 K. The UV–visible diffuse reflectance of3provides evidence of an LMCT band, supporting a mechanism of thermally activated LMCT quenching of Eu(III) emitting states. A series of ten isomorphous, trivalent lanthanide complexes of type Ln[N(SPPh2)2]3(Ln = Eu (3) Pr (4), Nd (5), Sm (6), Gd (7), Tb (8)) and Ln[N(SePPh2)2]3(Ln = Pr (9), Nd (10, structure was previously reported), Sm (11), and Gd (12) for Q = Se) were also synthesized and structurally characterized. These complexes for Ln = Pr, Nd, Sm, and Tb exhibited room temperature luminescence. This study provides examples of temperature-dependent luminescence of both Eu2+and Eu3+, and the use of soft-atom donor ligands to sensitize lanthanide luminescence in a range of trivalent lanthanides, spanning near IR and visible emitters.