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.
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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DOI：
10.1002/chem.200701852
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发表时间：
2008-06
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影响因子：
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通讯作者：
Biing‐Chiau Tzeng;Tse-Hao Chiu;Bo-So Chen;Gene-Hsiang Lee
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文献类型：
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作者：
Biing‐Chiau Tzeng;Tse-Hao Chiu;Bo-So Chen;Gene-Hsiang Lee
配体L1和L2‘(L1=N，N’，N‘’-三(4-吡啶基)三甲基酰胺，L2‘=N，N’，N‘’-tris(3-pyridinyl)-1，3，5-benzenetricarboxamide)属于一个有趣的具有C(3)-对称性的三吡啶三酰胺家族)被用来构建三维多孔或氢键骨架。通过一种新的单晶到单晶阴离子交换过程，在ClO(4)(-)阴离子存在下，[Cd(L1)(2)(ClO(4))(2)](N)(1c)可以从[Cd(L1)(2)Cl(2)](N)(1b)得到。这种阴离子交换过程具有很高的选择性，只能用ClO(4)(-)或Pf(6)(-)取代Cl(-)，而不能用BPh(4)(-)取代。这表明交换过程取决于阴离子的大小相对于主体材料中空穴的大小(约7.5A)。此外，还用粉末X射线衍射(PXRD)、元素分析(EA)和红外吸收光谱(IR)研究了1b的阴离子交换性质。结构上，[Zn(L1)(NO(3))(2)](N)(2)是由五配位的锌(II)离子组成的二维配位网络。令人惊讶的是，不同的三角-双锥体锌(II)离子传播形成不同的片状结构A和B，它们以A-B-A-B的方式堆积在晶格中，这些结构是氢键形成的3D延伸框架。[CuI(L2‘)](N)(3)的分子结构表明，Cu(I)离子为扭曲的四面体构型，3还形成了二维配位网络。值得注意的是，这个2D配位网络通过三重氢键和pi…pi相互作用进一步组装成一个显著的3D同手性骨架。所有这些三维配位聚合物和/或氢键骨架都是在固态下发光的，它们的固态发光性质已经在室温和/或77K下进行了研究。
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)(ClO(4))(2)](n) (1c) can be obtained from [Cd(L1)(2)Cl(2)](n) (1b) in the presence of ClO(4)(-) anions. This anion-exchange process is highly selective and only the substitution of Cl(-) by ClO(4)(-) or PF(6)(-) could be realized; Cl(-) was found not to be substituted by BPh(4)(-). 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 A). In addition, the anion-exchange properties of 1 b have also been investigated by means of powder X-ray diffraction (PXRD), elemental analysis (EA), and infrared absorption spectroscopy (IR). Structurally, [Zn(L1)(NO(3))(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...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.