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首页> 外文期刊>Chemistry: A European journal >Novel single-crystal-to-single-crystal anion exchange and self-assembly of luminescent d(10) metal (Cd-II, Zn-II, and Cu-I) complexes containing C-3-symmetrical ligands
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Novel single-crystal-to-single-crystal anion exchange and self-assembly of luminescent d(10) metal (Cd-II, Zn-II, and Cu-I) complexes containing C-3-symmetrical ligands

机译：新型的单晶至单晶阴离子交换和包含C-3-对称配体的发光d（10）金属（Cd-II，Zn-II和Cu-I）配合物的自组装

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摘要

Ligands L1 and L2' (L1= N,N',N ''-tris(4-pyridyl)trimesic amide, L2'= N,N,N ''-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide) belonging to an interesting family of tripyridyltriamides with C-3-symmetry have been utilized to construct 3D porous or hydrogen-bonded frameworks. Through a novel single-crystal-to-single-crystal anion-exchange process, [Cd(L1)(2)-(CIO4)(2)](n) (1c) can be obtained from [Cd(L1)(2)Cl-2](n) (1b) in the presence of ClO4- anions. This anion-exchange process is highly selective and only the substitution of Cl- by ClO4- or PF6- could be realized; Cl- was found not to be substituted by BPh4-. This demonstrates that the exchange process depends on the size of the anions in relation to the size of the cavities in the host material (ca. 7.5 angstrom). In addition, the anion-exchange properties of 1b have also been investigated by means of powder X-ray diffraction (PXRD), elemental analysis (EA), and infrared absorption spectroscopy (IR). Structurally, [Zn(L1)(NO3)(2)](n) (2) consists of a 2D coordination network with five-coordinate Zn-II ions. Surprisingly, different trigonal-bipyramidal Zn-II ions propagate to form distinct respective sheet structures, A and B, which are packed in an A-B-A-B manner in the crystal lattice, and these are hydrogen-bonded to give a 3D extended framework. The molecular structure of [CuI(L2')](n) (3) shows that the Cu-I ion adopts a distorted tetrahedral geometry and 3 also forms a 2D coordination network. Significantly, this 2D coordination network is further assembled into a remarkable 3D homochiral framework through triple hydrogen bonding and pi center dot center dot center dot pi interactions. All of these 3D coordination polymers and/or hydrogen-bonded frameworks are luminescent in the solid state, and their solid-state luminescent properties have been investigated at room temperature and/or at 77 K.
机译：配体L1和L2'（L1 = N，N'，N''-三（4-吡啶基）三甲酰胺，L2'= N，N，N''-三（3-吡啶基）-1,3,5-属于有趣的具有C-3-对称性的三吡啶基三酰胺家族的苯三甲酰胺）已被用于构建3D多孔或氢键构架。通过新颖的单晶至单晶阴离子交换过程，可以从[Cd（L1）（2）获得[Cd（L1）（2）-（CIO4）（2）]（n）（1c）。 ）Cl-2]（n）（1b）在ClO4-阴离子的存在下。这种阴离子交换过程是高度选择性的，只能实现用ClO4-或PF6-取代Cl-。发现Cl-未被BPh4-取代。这表明交换过程取决于阴离子的大小与基质材料中空穴的大小（约7.5埃）有关。此外，还通过粉末X射线衍射（PXRD），元素分析（EA）和红外吸收光谱（IR）研究了1b的阴离子交换性能。在结构上，[Zn（L1）（NO3）（2）]（n）（2）由具有五配位Zn-II离子的2D配位网络组成。出乎意料的是，不同的三角-双锥体Zn-II离子传播以形成各自不同的片状结构A和B，它们以A-B-A-B方式堆积在晶格中，并且通过氢键键合形成3D扩展骨架。 [CuI（L2'）]（n）（3）的分子结构表明，Cu-I离子采用扭曲的四面体几何形状，而3也形成2D配位网络。重要的是，该2D配位网络通过三氢键和pi中心点中心点中心点pi相互作用进一步组装成了出色的3D同手性框架。所有这些3D配位聚合物和/或氢键合骨架均处于固态发光状态，并且已在室温和/或77 K下研究了其固态发光性能。

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