Kitagawa Yuichi, Kumagai Marina, Ferreira da Rosa Pedro Paulo, Fushimi Koji, Hasegawa Yasuchika
Faculty of Engineering, Hokkaido University, Kita-13 Jo, Nishi-8 Chome, Kita-ku, Sapporo, Hokkaido, 060-8628, Japan.
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita-21 Jo, Nishi-10 Chome, Kita-ku, Sapporo, Hokkaido, 001-0021, Japan.
Chemistry. 2021 Jan 4;27(1):264-269. doi: 10.1002/chem.202002628. Epub 2020 Nov 9.
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 Eu and Gd , 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 Gd ion in the Eu -Gd polymer. The emission quantum yield and the maximum relative temperature sensitivity (S ) of emission lifetimes for the Eu -Gd polymer (Eu:Gd=1:1, Φ =52 %, S =3.73 % K ) were higher than those for the pure Eu coordination polymer (Φ =36 %, S =2.70 % K ), respectively. Enhanced temperature sensing properties are caused by control of long-range electronic coupling based on phosphine oxide with chrysene framework.
提出了一种基于镧系配位聚合物中长程电子耦合的高效分子发光温度计设计。该配位聚合物由镧系离子铕（Eu）和钆（Gd）、三种阴离子配体（六氟乙酰丙酮）以及基于并四苯的氧化膦桥（6,12-双（二苯基磷酰基）并四苯）组成。单聚合物链的锯齿形取向诱导形成了包含多个用于CH-F分子间相互作用位点的堆积配位结构，从而导致热稳定性高于350°C。通过改变Eu-Gd聚合物中Gd离子的浓度来控制电子耦合。Eu-Gd聚合物（Eu:Gd = 1:1，Φ = 52%，S = 3.73% K）的发射量子产率和发射寿命的最大相对温度灵敏度（S）分别高于纯Eu配位聚合物（Φ = 36%，S = 2.70% K）。基于并四苯骨架的氧化膦对长程电子耦合的控制导致了温度传感性能的增强。
