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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Two new zinc(II) coordination complexes with helix characteristics showing both interpenetration and self-catenation features: a platform for the synthesis of chiral and catenated structures assembled by length-modulated dicarboxylates
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Two new zinc(II) coordination complexes with helix characteristics showing both interpenetration and self-catenation features: a platform for the synthesis of chiral and catenated structures assembled by length-modulated dicarboxylates

机译：具有螺旋特征的两种新型锌（II）配位配合物同时显示互穿和自连接特征：一个由长度调节的二羧酸盐组装而成的手性和链状结构的合成平台

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Two new zinc coordination complexes, namely [Zn_2(tib)_(4/3)(L~1)_2]·DMA (1) and [Zn_2(tib)_(4/3)(L~2)_2]·H_2O (2) (tib = 1,3,5-tris(1-imidazolyl)benzene, H_2L~1 = biphenyl-4,4'-dicarboxylic acid, H_2L~2 = 4,4'-(2,2'-oxybis- (ethane-2,1-diyl)bis(oxy))dibenzoic acid and DMA = N,N-dimethylacetamide), are obtained using achiral mixed ligands and characterized using elemental analysis, IR and X-ray crystallography. Compounds 1 and 2 both display intriguing structural features of both interpenetration and self-catenation. By careful inspection of the two structures, we found that the Zn(II) cations, the tib ligands, and the dicarboxylic anions show the same coordination modes or analogous configurations. Compound 1 is chiral, which was confirmed by measuring the optical rotation of the bulk samples using solid-state circular dichroism (CD). It is comprised of two crystallographically independent interpenetrated 3D motifs, each containing interlaced triple-stranded right- and left-handed Zn-L~1-Zn helical chains and chiral 2D [Zn(tib)_(2/3)] layers. Both motifs display binodal (3,4)-coordinated 3D self-catenated networks with the point symbol (10~3)_2(10~6)_3 and the vertex symbols [10_(13)·10_(13)·10_(13)] and [10_7·10_7·10_8·10_(10)·10_(11)·10_(11)]. However, the two types of helical chains are not racemic due to the differences between the two kinds of L~1 anions, and the two types of chiral 2D [Zn(tib)_(2/3)]~(2+) layers are not enantiomeric either due to the different configurations of the tib ligands. Therefore, the two motifs are not enantiomers. Compound 2 is achiral, containing Zn-L~2-Zn zigzag chains that span into three directions and chiral 2D [Zn(tib)_(2/3)] layers. The overall 3D network is a new binodal (3,4)-coordinated self-catenated network with the point symbol (10~3)_2(10~6)_3 and the vertex symbols [10_7·10_7·10_7] and [10_2·10_4·10_5·10_5·10_5·10_5]. Two of these networks interpenetrate. Their chiral and achiral structures are mainly modulated by the length of the dicarboxylates. As expected, compounds 1 and 2 show photoluminescence behaviors and compound 1 shows a ferroelectric behavior. Thermogravimetric studies of 1 and 2 have also been performed. We examined all 48 known structures containing the tib ligand and drew the conclusion that the metal + tib combination, modulated by the prolonged L ligands, can be a good basis for new chiral and catenated structures.
机译：两种新的锌配位化合物，即[Zn_2（tib）_（4/3）（L〜1）_2]·DMA（1）和[Zn_2（tib）_（4/3）（L〜2）_2]· H_2O（2）（tib = 1,3,5-三（1-咪唑基）苯，H_2L〜1 =联苯-4,4'-二羧酸，H_2L〜2 = 4,4'-（2,2'-使用非手性混合配体获得氧双（乙烷-2,1-二基）双（氧））二苯甲酸和DMA = N，N-二甲基乙酰胺，并使用元素分析，IR和X射线晶体学进行表征。化合物1和2都显示出互穿和自连接的有趣结构特征。通过仔细检查这两个结构，我们发现Zn（II）阳离子，tib配体和二羧酸根阴离子显示出相同的配位模式或相似的构型。化合物1是手性的，这可以通过使用固态圆二色性（CD）测量块状样品的旋光度来确认。它由两个晶体学上独立的互穿3D图案组成，每个图案都包含交错的三链右手和左手Zn-L〜1-Zn螺旋链和手性2D [Zn（tib）_（2/3）]层。这两个主题都显示具有点符号（10〜3）_2（10〜6）_3和顶点符号[10_（13）·10_（13）·10_（13）的与坐标轴（3,4）协调的3D自分类网络。 ）]和[10_7·10_7·10_8·10_（10）·10_（11）·10_（11）]。然而，由于两种L〜1阴离子和两种手性2D [Zn（tib）_（2/3）]〜（2+）层之间的差异，两种螺旋链不是消旋的由于tib配体的不同构型，它们不是对映体。因此，这两个基序不是对映体。化合物2是非手性的，包含横跨三个方向的Zn-L〜2-Zn之字形链和手性二维[Zn（tib）_（2/3）]层。整个3D网络是具有点符号（10〜3）_2（10〜6）_3和顶点符号[10_7·10_7·10_7]和[10_2· 10_4·10_5·10_5·10_5·10_5]。这些网络中的两个相互渗透。它们的手性和非手性结构主要受二羧酸盐的长度调节。正如预期的那样，化合物1和2显示出光致发光行为，化合物1显示出铁电行为。还进行了1和2的热重研究。我们检查了所有48种含有tib配体的已知结构，并得出结论：经延长的L配体调节的金属+ tib组合可以成为新的手性和链状结构的良好基础。

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