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Thermo- and photo-modulation of exciplex fluorescence in a 3D spin crossover Hofmann-type coordination polymer†
Chemical Science ( IF 7.6 ) Pub Date : 2018-09-11 00:00:00 , DOI: 10.1039/c8sc02677g
Teresa Delgado 1 , Manuel Meneses-Sánchez 2 , Lucía Piñeiro-López 2 , Carlos Bartual-Murgui 2 , M Carmen Muñoz 3 , José Antonio Real 2
Affiliation  

The search for bifunctional materials showing synergies between spin crossover (SCO) and luminescence has attracted substantial interest since they could be promising platforms for new switching electronic and optical technologies. In this context, we present the first three-dimensional FeII Hofmann-type coordination polymer exhibiting SCO properties and luminescence. The complex {FeII(bpben)[Au(CN)2]}@pyr (bpben = 1,4-bis(4-pyridyl)benzene) functionalized with pyrene (pyr) guests undergoes a cooperative multi-step SCO, which has been investigated by single crystal X-ray diffraction, single crystal UV-Vis absorption spectroscopy, and magnetic and calorimetric measurements. The resulting fluorescence from pyrene and exciplex emissions are controlled by the thermal and light irradiation (LIESST effect) dependence of the high/low-spin state population of FeII. Conversely, the SCO can be tracked by monitoring the fluorescence emission. This ON–OFF interplay between SCO and luminescence combined with the amenability of Hofmann-type materials to be processed at the nano-scale may be relevant for the generation of SCO-based sensors, actuators and spintronic devices.

中文翻译:


3D 自旋交叉霍夫曼型配位聚合物中激基复合物荧光的热调制和光调制†



对显示自旋交叉(SCO)和发光之间协同作用的双功能材料的研究引起了人们的极大兴趣,因为它们可能成为新的开关电子和光学技术的有前途的平台。在此背景下,我们提出了第一个具有 SCO 特性和发光特性的三维 Fe II霍夫曼型配位聚合物。用芘 (pyr) 客体功能化的复合物 {Fe II (bpben)[Au(CN) 2 ]}@pyr (bpben = 1,4-双(4-吡啶基)苯) 经历了协同多步 SCO,通过单晶 X 射线衍射、单晶紫外-可见吸收光谱以及磁和量热测量进行了研究。芘和激基复合物发射产生的荧光由 Fe II的高/低自旋态布居的热和光照射(LIESST 效应)依赖性控制。相反,可以通过监测荧光发射来跟踪 SCO。 SCO 和发光之间的这种开关相互作用,加上霍夫曼型材料在纳米尺度上加工的适应性,可能与基于 SCO 的传感器、执行器和自旋电子器件的产生相关。
更新日期:2018-09-11
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