Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, Poland.
Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA.
Dalton Trans. 2019 Nov 7;48(41):15493-15500. doi: 10.1039/c9dt02164g. Epub 2019 Jul 11.
Four new three-dimensional (3-D) coordination frameworks based on the heptacyanomolybdate(iii) anion were prepared and characterised by magnetic measurements: {[Mn(imH)][Mn(HO)(imH)][Mn(imH)] [Mo(CN)]·6HO} (1) (imH = imidazole), {[Mn(HO)(imH)][Mn(HO)(imH)][Mo(CN)]·5HO} (2), {[Mn(Htrz)(HO)][Mn(Htrz)(HO)][Mo(CN)]·5.6HO} (3) (Htrz = 1,2,4-triazole) and {[Mn(HO)][Mn(HO)][Mo(CN)]·6HO·2urea} (4). All four compounds exhibit long-range ferrimagnetic ordering and exhibit an opening of their magnetic hysteresis loops at 1.8 K; 1 and 2 exhibit the highest coercive fields among all known [Mo(CN)]-based assemblies, 5000 and 4500 Oe respectively. The coercivity of 1-4 is correlated with the geometry of the heptacyanomolybdate(iii) anion and the cyanide bridging pattern. A paramagnetic analogue of compound 1, {[Mn(imH)][Mn(HO)(imH)][Mn(imH)][Re(CN)]·6HO} (1Re), where the heptacyanomolybdate(iii) anion is substituted by the diamagnetic heptacyanorhenate(iii) anion is also reported which constitutes the first example of a coordination framework based on [Re(CN)].
基于七氰合钼(III)阴离子，我们制备了四个新的三维（3-D）配位框架，并通过磁性测量对其进行了表征：{[Mn(imH)][Mn(HO)(imH)][Mn(imH)] [Mo(CN)]·6HO}（1）（imH=咪唑）、{[Mn(HO)(imH)][Mn(HO)(imH)][Mo(CN)]·5HO}（2）、{[Mn(Htrz)(HO)][Mn(Htrz)(HO)][Mo(CN)]·5.6HO}（3）（Htrz=1,2,4-三唑）和{[Mn(HO)][Mn(HO)][Mo(CN)]·6HO·2urea}（4）。所有四个化合物都表现出长程亚铁磁有序，并在 1.8 K 时表现出磁滞回线的打开；1 和 2 分别表现出所有已知基于[Mo(CN)]组装体中最高的矫顽场，分别为 5000 和 4500 Oe。1-4 的矫顽力与七氰合钼(III)阴离子的几何形状和氰桥连接模式有关。化合物 1 的顺磁类似物，{[Mn(imH)][Mn(HO)(imH)][Mn(imH)][Re(CN)]·6HO}（1Re），其中七氰合钼(III)阴离子被抗磁性的七氰合铼(III)阴离子取代，这也是第一个基于[Re(CN)]的配位框架的例子。
