Palacios-Corella Mario, Fernández-Espejo Alejandro, Bazaga-García Montse, Losilla Enrique R, Cabeza Aurelio, Clemente-León Miguel, Coronado Eugenio
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia , Catedrático José Beltrán 2, 46980 Paterna, Spain.
Departamento de Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias, Universidad de Málaga , Campus de Teatinos s/n, 29071 Málaga, Spain.
Inorg Chem. 2017 Nov 20;56(22):13865-13877. doi: 10.1021/acs.inorgchem.7b01965. Epub 2017 Nov 1.
The syntheses, structures, magnetic, and proton conductivity properties of a family of bimetallic anilate-based compounds with inserted alkylammonium cations are presented. The structures of (MeNH)[MnCr(BrAn)]·2HO (1), (EtNH)[MnCr(BrAn)] (2), (EtNH)[MnCr(ClAn)] (3), and [(Et)(i-Pr)NH][MnCr(BrAn)]·(CHCl)·(HO) (4) contain a 2D anionic network formed by Mn(II) and Cr(III) ions linked through anilate ligands. In 1, 2, and 3, the hexagonal holes of this network are occupied by MeNH, EtNH, or EtNH cations. Interestingly, the small increase of size of the templating cation in 4 ([(Et)(i-Pr)NH] in the place of MeNH, EtNH or EtNH), gives rise to a different structure with half of the cations placed within the layers and the other one in the space between the layers. This leads to bilayers with an interlayer separation similar to those of 1, 2, and 3 separated by larger interbilayer distances. Compounds 1, 2, and 3 show a ferrimagnetic ordering with a T of 8.0 K (1), 8.9 K (2), and 8.0 K (3). In 4, the presence of different interlayer distances leads to a metamagnetic behavior when the sample is measured in contact with the mother liquor. The behavior changes in the dry sample, which shows a ferrimagnetic ordering as that of 1, 2, and 3 due to collapse of the structure as confirmed by powder X-ray diffraction. Interestingly, the metamagnetic behavior is recovered after reimmersing the crystals in the mother liquor proving the reversibility of the process. All solids are Grotthuss-type proton conductors with conductivity values ranging between 2.3 × 10 S·cm for 3 and 2.4 × 10 S·cm for 1 measured at 70 °C and 95% relative humidity and activation energies of ∼0.2 eV.
本文介绍了一系列插入烷基铵阳离子的双金属苯胺基化合物的合成、结构、磁性和质子传导性质。(MeNH)[MnCr(BrAn)]·2HO (1)、(EtNH)[MnCr(BrAn)] (2)、(EtNH)[MnCr(ClAn)] (3) 和 [(Et)(i-Pr)NH][MnCr(BrAn)]·(CHCl)·(HO) (4) 的结构包含由通过苯胺配体连接的Mn(II) 和Cr(III) 离子形成的二维阴离子网络。在1、2和3中，该网络的六边形孔被MeNH、EtNH或EtNH阳离子占据。有趣的是，4中模板阳离子尺寸的小幅增加（用[(Et)(i-Pr)NH]取代MeNH、EtNH或EtNH）导致了不同的结构，其中一半阳离子位于层内，另一半位于层间空间。这导致了双层结构，其层间间距与1、2和3相似，但被更大的双层间距隔开。化合物1、2和3表现出亚铁磁有序，居里温度分别为8.0 K (1)、8.9 K (2) 和8.0 K (3)。在4中，当样品与母液接触测量时，不同的层间距离导致了变磁行为。干燥样品的行为发生了变化，由于结构坍塌，其表现出与1、2和3相同的亚铁磁有序，粉末X射线衍射证实了这一点。有趣的是，将晶体重新浸入母液后，变磁行为得以恢复，证明了该过程的可逆性。所有固体都是Grotthuss型质子导体，在70°C和95%相对湿度下测量，电导率值在3的2.3×10 S·cm到1的2.4×10 S·cm之间，活化能约为0.2 eV。
