Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov Street, 420088 Kazan, Russia.
Centre for Optical and Laser Materials Research, Research Park of Saint Petersburg State University, 5 Ulianovskaya Street, 198504 Saint Petersburg, Russia.
Molecules. 2023 Jan 10;28(2):706. doi: 10.3390/molecules28020706.
Tertiary diethylpyridylphosphine was synthesized by the reaction of pyridylphosphine with bromoethane in a suberbasic medium. The reaction of phosphine with the copper(I) iodide led to the formation of a copper(I) coordination polymer, which, according to the X-ray diffraction data, has an intermediate structure with a copper-halide core between the octahedral and stairstep geometries of the CuI clusters. The obtained coordination polymer exhibits a green emission in the solid state, which is caused by the (M+X)LCT transitions. The heating up of the copper(I) coordination polymer to 138.5 °C results in its monomerization and the formation of a new solid-state phase. The new phase exhibits a red emission, with the emission band maximum at 725 nm. According to the experimental data and quantum chemical computations, it was concluded that depolymerization probably leads to a complex that is formed with the octahedral structure of the copper-halide core. The resulting solid-state phase can be backward-converted to the polymer phase via recrystallization from the acetone or DMF. Therefore, the obtained coordination polymer can be considered a sensor or detector for the overheating of processes that should be maintained at temperatures below 138 °C (e.g., engines, boiling liquids, solar heat systems, etc.).
叔丁基二乙基膦通过在碱性介质中吡啶基膦与溴乙烷的反应合成。膦与碘化亚铜的反应导致形成铜(I)配位聚合物,根据 X 射线衍射数据,该配位聚合物具有具有介于八面体和阶梯状 CuI 簇的铜-卤核之间的中间结构。所得配位聚合物在固态中表现出绿色发射,这是由(M+X)LCT 跃迁引起的。将铜(I)配位聚合物加热至 138.5°C 会导致其单体化并形成新的固态相。新相表现出红色发射,发射带的最大值在 725nm 处。根据实验数据和量子化学计算,得出结论,解聚可能导致形成具有铜-卤核的八面体结构的配合物。所得固态相可以通过从丙酮或 DMF 重结晶返回到聚合物相。因此,所得到的配位聚合物可以被认为是用于需要保持在 138°C 以下的温度的过程(例如发动机、沸腾液体、太阳能热系统等)的过热的传感器或探测器。