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Long-range LMCT coupling in Eu(III) coordination polymers for an effective molecular luminescent thermometer.
Chemistry - A European Journal ( IF 4.3 ) Pub Date : 2020-07-03 , DOI: 10.1002/chem.202002628
Yuichi Kitagawa 1, 2 , Marina Kumagai 3 , Pedro Paulo Ferreira da Rosa 3 , Koji Fushimi 1 , Yasuchika Hasegawa 1, 2
Affiliation  

A design for an effective molecular luminescent thermometer based on long‐range electronic coupling in lanthanide coordination polymers is proposed. The coordination polymers are composed of lanthanide ions EuIII and GdIII, three anionic ligands (hexafluoroacetylacetonate), and a chrysene‐based phosphine oxide bridges (6,12‐bis(diphenylphosphoryl)chrysene). The zig‐zag orientation of the single polymer chains induces the formation of packed coordination structures containing multiple sites for CH‐F intermolecular interactions, resulting in thermal stability above 350 °C. The electronic coupling is controlled by changing the concentration of the GdIII ion in the EuIII‐GdIII polymer. The emission quantum yield and the maximum relative temperature sensitivity (Sm) of emission lifetimes for the EuIII‐GdIII polymer (Eu:Gd=1:1, Φtot=52 %, Sm=3.73 % K−1) were higher than those for the pure EuIII coordination polymer (Φtot=36 %, Sm=2.70 % K−1), respectively. Enhanced temperature sensing properties are caused by control of long‐range electronic coupling based on phosphine oxide with chrysene framework.

中文翻译:

Eu(III)配位聚合物中的长距离LMCT耦合用于有效的分子发光温度计。

提出了一种基于长距离电子耦合的镧系配位聚合物的有效分子发光温度计的设计。配位聚合物由镧系元素离子Eu III和Gd III,三个阴离子配体(六氟乙酰丙酮酸酯)和一个基于丙烯的氧化膦桥(6,12-双(二苯基磷酰基)丙烯)组成。单个聚合物链的之字形取向诱导形成堆积的配位结构,其中包含多个CH-F分子间相互作用的位点,从而在350°C以上具有热稳定性。通过改变Eu III -Gd III中Gd III离子的浓度来控制电子耦合聚合物。发射量子产率和最大相对温度敏感性(小号发射寿命为Eu)的III -Gd III聚合物(EU:GD = 1:1,Φ TOT = 52%,小号= 3.73%K -1)是比为纯的Eu更高III的配位聚合物(Φ TOT = 36%,小号= 2.70%K -1分别)。温度控制特性的增强是由于控制了基于氧化膦和骨架的远程电子耦合而引起的。
更新日期:2020-07-03
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