Jayaratna Naleen B, Cowan Matthew G, Parasar Devaborniny, Funke Hans H, Reibenspies Joseph, Mykhailiuk Pavel K, Artamonov Oleksii, Noble Richard D, Dias H V Rasika
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX, 76019, USA.
Department of Chemical and Process Engineering, University of Canterbury, Christchurch, 8140, New Zealand.
Angew Chem Int Ed Engl. 2018 Dec 10;57(50):16442-16446. doi: 10.1002/anie.201810460. Epub 2018 Nov 15.
The trinuclear copper(I) pyrazolate complex [Cu ] rearranges to the dinuclear analogue [Cu ⋅(C H ) ] when exposed to ethylene gas. Remarkably, the [Cu ]↔[Cu ⋅(C H ) ] rearrangement occurs reversibly in the solid state. Furthermore, this transformation emulates solution chemistry. The bond-making and breaking processes associated with the rearrangement in the solid-state result in an observed heat of adsorption (-13±1 kJ mol per Cu-C H interaction) significantly lower than other Cu-C H interactions (≥-24 kJ mol ). The low overall heat of adsorption, "step" isotherms, high ethylene capacity (2.76 mmol g ; 7.6 wt % at 293 K), and high ethylene/ethane selectivity (136:1 at 293 K) make [Cu ] an interesting basis for the rational design of materials for low-energy ethylene/ethane separations.
三核铜（I）吡唑酸盐配合物[Cu]在暴露于乙烯气体时会重排为双核类似物[Cu·(C₂H₄)]。值得注意的是，[Cu]↔[Cu·(C₂H₄)]重排在固态下是可逆发生的。此外，这种转变模拟了溶液化学。与固态重排相关的键形成和断裂过程导致观察到的吸附热（每个Cu-C₂H₄相互作用为-13±1 kJ mol）明显低于其他Cu-C₂H₄相互作用（≥-24 kJ mol）。低的总吸附热、“阶梯”等温线、高乙烯容量（2.76 mmol g；在293 K时为7.6 wt %）以及高乙烯/乙烷选择性（在293 K时为136:1）使得[Cu]成为合理设计用于低能量乙烯/乙烷分离材料的有趣基础。
