A porous Cu(II)-MOF containing [PW12O40](3-) and a large protonated water cluster: synthesis, structure, and proton conductivity

作者：Wei, Meilin^*; Chen, Lin; Duan, Xianying

来源：Journal of Coordination Chemistry, 2014, 67(17): 2809-2819.

DOI：10.1080/00958972.2014.957689

• 4,4 '-Bipyridine-N,N '-dioxide
• Crystal structure
• Proton conductivity
• Polyoxometalates
• Metal-organic framework

A proton-conducting metal-organic framework (MOF), {[Cu-4(dpdo)(12)][H(H2O)(27)(CH3CN)(12)][PW12O40](3)}(n) (where dpdo is 4,4 '-bipyridine-N,N '-dioxide) (1), was synthesized by the reaction of CuHPW(12)O(40)Greek ano teleianH(2)O and dpdo at room temperature. Single-crystal X-ray diffraction analysis at 293 K revealed that 1 crystallized in the cubic space group Im-3 and presented a non-interwoven 3-D framework with cubic cavities and guest molecules. A large ionic water cluster H+(H2O)(27), consisting of a water shell (H2O)(26) and an encaged H+(H2O) as a center core, was trapped in the cubic cavity of the MOF {[Cu-4(dpdo)(12)(PW12O40)(3)](-)}(infinity). Thermogravimetric analysis suggests that 1 has high thermal stability, indicating that such a non-interwoven 3-D framework with cubic cavities is a suitable host for researching protonated water clusters. Its water vapor adsorption isotherm at room temperature and pressure shows that the water vapor adsorbed in it was 65.1cm(3 )g(-1) at the maximum allowable humidity. It exhibits good proton conductivities of 10(-5)-10(-4 )S( )cm(-1) at 100 degrees C in the relative humidity range 35-98%.

• 出版日期2014-9-2
• 单位河南师范大学