基于Cu(I)的配合物具有成本便宜和发光寿命长等有利于荧光传感的独到优势。但是,大部分Cu(Ⅰ)配合物在空气中不稳定,易被氧气氧化,或者比较难形成多孔框架。在沸石型咪唑锌多孔配位聚合物中,RHO-[Zn(eim)_2](MAF-6,Heim=2-ethylimidazole)由于其较大的孔径和优异的疏水特性而备受关注。本文利用Cu(I)离子与Zn(Ⅱ)离子相似的配位习性,用Cu(I)离子部分取代MAF-6中的Zn(II)离子,得到同构的磷光多孔配位聚合物Cu:MAF-6。该材料在极低氧气压力环境(〈600 Pa)中表现出非常灵敏的氧气荧光传感性能(Ksv=28.09 k Pa~(-1);检测限0.36 Pa)。
sensing, Cu(I)-based coordination complexes have unique advantages such as low cost and long luminescence lifetime. However, Cu(I) coordination complexes are generally unstable in air, easily oxidized by oxygen, or quite difficult to form porous frameworks. Among various zeolitic zinc- imidazolate porous coordination polymers, RHO-[ Zn(eim) 2 ] ( MAF-6, Helm = 2-ethylimidazole ) has received considerable interest due to its large pore size and superior hydrophobicity. In this paper, by virtue of the similar coordination behaviors of Cu(I) and Zn( Ⅱ ) ions, an isomorphic phosphorescent porous coordination polymer, Cu: MAF-6, was obtained through partial substituting Zn( Ⅱ ) ions of MAF-6 with Cu ( I ) ions. The phosphorescence of Cu: MAF-6 exhibits very high oxygen sensitivity ( Ksv = 28.09 kPa-1 ; limit of detection =0. 36 Pa) in the low oxygen concentration environment( 〈600 Pa). Keywords copper( I); oxygen sensing; zeolite; imidazole; porous coordination polymer; metal-organic framework