Mon Marta, Vallejo Julia, Pasán Jorge, Fabelo Oscar, Train Cyrille, Verdaguer Michel, Ohkoshi Shin-Ichi, Tokoro Hiroko, Nakagawa Kosuke, Pardo Emilio
Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMol). Universitat de València, 46980 Paterna, València, Spain.
Dalton Trans. 2017 Nov 7;46(43):15130-15137. doi: 10.1039/c7dt03415f.
A novel three-dimensional (3D) coordination polymer with the formula (CNH)[MnCr(ox)]·5HO (2), where ox = oxalate and CNH = imidazolium cation, is reported. Single crystal X-ray diffraction reveals that this porous coordination polymer adopts a chiral three-dimensional quartz-like architecture, with the guest imidazolium cations and water molecules being hosted in its pores. This novel multifunctional material exhibits both a ferromagnetic ordering at T = 3.0 K, related to the host MnCr network, and high proton conductivity [1.86 × 10 S cm at 295 K and 88% relative humidity (RH)] due to the presence of the acidic imidazolium cations and free water molecules. The similarity of the structure of compound 2 to that of the previously reported analogous compound (NH)[MnCr(ox)]·4HO, (1), also allows us to analyse, to a certain extent, the effect of the acidity of the proton donating guest molecules on proton conduction properties. 2 hosts, in one-dimensional (1D) channels, imidazolium cations, which are more acidic than the ammonium ones in 1 and, as a consequence, 2 shows higher proton conduction than 1, highlighting the effect of the pK of the proton donating guest molecules on proton conductivity.
报道了一种新型三维(3D)配位聚合物,其化学式为(CNH)[MnCr(ox)]·5HO(2),其中ox = 草酸根,CNH = 咪唑阳离子。单晶X射线衍射表明,这种多孔配位聚合物采用手性三维石英状结构,客体咪唑阳离子和水分子容纳在其孔中。这种新型多功能材料在T = 3.0 K时表现出铁磁有序,这与主体MnCr网络有关,并且由于酸性咪唑阳离子和游离水分子的存在,具有高质子传导率[在295 K和88%相对湿度(RH)下为1.86×10 S cm]。化合物2与先前报道的类似化合物(NH)[MnCr(ox)]·4HO(1)的结构相似性,也使我们能够在一定程度上分析供质子客体分子的酸度对质子传导性能的影响。2在一维(1D)通道中容纳咪唑阳离子,其酸性比1中的铵阳离子更强,因此,2显示出比1更高的质子传导率,突出了供质子客体分子的pK对质子传导率的影响。