Benmansour Samia, Vallés-García Cristina, Gómez-Claramunt Patricia, Mínguez Espallargas Guillermo, Gómez-García Carlos J
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, 2, 46980 Paterna, Valencia, Spain.
Inorg Chem. 2015 Jun 1;54(11):5410-8. doi: 10.1021/acs.inorgchem.5b00451. Epub 2015 May 12.
The similar bis-bidentate coordination mode of oxalato and anilato-based ligands is exploited here to create the first examples of 2D and 3D heterometallic lattices based on anilato ligands combining M(I) and a M(III) ions, phases already observed with oxalato but unknown with anilato-type ligands. These lattices are prepared with alkaline metal ions and magnetic chiral tris(anilato)metalate molecular building blocks: M(III)(C6O4X2)3 (M(III) = Fe and Cr; X = Cl and Br; (C6O4X2)(2-) = dianion of the 3,6-disubstituted derivatives of 2,5-dihydroxy-1,4-benzoquinone, H4C6O4). The new compounds include two very similar 2D lattices formulated as (PBu3Me)2[NaCr(C6O4Br2)3] (1) and (PPh3Et)2KFe(C6O4Cl2)32 (2), both presenting hexagonal M(I)M(III)(C6O4X2)3 honeycomb layers with (PBu3Me)(+) in 1 or (PPh3Et)(+) and dmf in 2 inserted between them. Minor modifications in the synthetic conditions yield the novel 3D lattice (NEt3Me)[Na(dmf)][NaFe(C6O4Cl2)3] (3), in which hexagonal layers analogous to 1 and 2 are interconnected through Na(+) cations, and (NBu3Me)2[NaCr(C6O4Br2)3] (4), the first heterometallic 3D lattice based on anilato ligands. This compound presents two interlocked chiral 3D (10,3) lattices with opposite chiralities. Attempts to prepare 4 in larger quantities result in the 2D polymorph of compound 4 (4'). Magnetic properties of compounds 1, 3, and 4' are reported, and in all cases we observe, as expected, paramagnetic behaviors that can be satisfactorily reproduced with simple monomer models including a zero field splitting (ZFS) of the corresponding S = 3/2 for Cr(III) in 1 and 4' or S = 5/2 for Fe(III) in 3.
本文利用草酸根和苯胺酸基配体相似的双齿配位模式，首次制备了基于苯胺酸配体的二维和三维异金属晶格，其中包含M(I)和M(III)离子，这种相在用草酸根时已被观察到，但在苯胺酸型配体中尚属未知。这些晶格是用碱金属离子和磁性手性三(苯胺酸)金属酸盐分子构建块制备的：M(III)(C6O4X2)3（M(III)=Fe和Cr；X=Cl和Br；(C6O4X2)(2-)=2,5-二羟基-1,4-苯醌的3,6-二取代衍生物的二价阴离子，H4C6O4）。新化合物包括两种非常相似的二维晶格，化学式为(PBu3Me)2[NaCr(C6O4Br2)3]（1）和(PPh3Et)2KFe(C6O4Cl2)32（2），两者均呈现六边形M(I)M(III)(C6O4X2)3蜂窝层，1中插入(PBu3Me)(+)，2中插入(PPh3Et)(+)和dmf。合成条件的微小变化产生了新型三维晶格(NEt3Me)[Na(dmf)][NaFe(C6O4Cl2)3]（3），其中类似于1和2的六边形层通过Na(+)阳离子相互连接，以及(NBu3Me)2[NaCr(C6O4Br2)3]（4），这是基于苯胺酸配体的首个异金属三维晶格。该化合物呈现出两个具有相反手性的互锁手性三维(10,3)晶格。大量制备4的尝试得到了化合物4的二维多晶型物(4')。报道了化合物1、3和4'的磁性，在所有情况下，正如预期的那样，我们观察到顺磁行为，用简单的单体模型可以令人满意地再现，包括1和4'中Cr(III)相应S = 3/2或3中Fe(III)相应S = 5/2的零场分裂(ZFS)。
