Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi'an, 710069, PR China.
Dalton Trans. 2009 Dec 14(46):10181-91. doi: 10.1039/b909309e. Epub 2009 Oct 6.
This article represents a systematical investigation on the structures of silver(I) dicarboxylate incorporating secondary ligands, revealing that the secondary interactions could play an important role in interlinking low-dimensional entities to high-dimensional supramolecular frameworks. A new 2D silver(I) crystalline dicarboxylate, {Ag(6)(ADC)(3)(H(2)O)(1.5).5.18H(2)O}(n) (1) (H(2)ADC = 1,3-adamantanedicarboxylic acid), has been obtained by slow diffusion of corresponding precursors. To investigate the influence of the properties of pyridylic neutral ligands on the complex structures based on compound 1, five kinds of neutral ligands (bipy = 4,4'-bipyridine; bpa = 1,2-bis(4-pyridyl)ethane; bpe = 1,2-bis(4-pyridyl)ethene; bpp = 1,3-bis(4-pyridyl)propane; bpdap = N,N'-bis(3-pyridyl)-2,6-diaminopyridine) were selected, and a series of new silver(I) dicarboxylate have been synthesized: {[Ag(bpa)(HADC)]}(n) (2), {[Ag(bpp)(HADC)].CH(3)OH}(n) (3), {[Ag(4)(bpe)(3)(ADC)(2)].2H(2)O}(n) (4), {[Ag(bipy)(HADC)].H(2)O}(n) (5), {[Ag(2)(bipy)(2)(ADC)].6H(2)O}(n) (6), and [Ag(8)(bpdap)(4)(ADC)(4)].2C(2)H(5)OH.6H(2)O (7). Single-crystal X-ray structural analysis shows that complexes 1 and 4 are formed by hexanuclear and tetranuclear Ag(I) clusters with weak Ag-Ag interactions. Complexes 2 and 3 are dinuclear structures, 5 and 6 exhibit an infinite 1D chain structure, whereas 7 is a discrete octanuclear Ag(I) unit. The structures of 1-7 span from dinuclear, tetranuclear, hexanuclear, to octanuclear Ag(I) complexes, which indicates that secondary ligands do play important roles in the formation of such coordination architectures. Thermal stability, X-ray powder diffraction and luminescent properties of the compounds are also discussed.
本文对含有次级配体的银（I）二羧酸酯的结构进行了系统研究，表明次级相互作用在将低维实体连接成高维超分子框架方面起着重要作用。通过缓慢扩散相应的前体，得到了一种新的二维银（I）结晶二羧酸酯，{Ag(6)(ADC)(3)(H2O)(1.5).5.18H2O}(n)（1）（H2ADC = 1,3-金刚烷二羧酸）。为了研究基于化合物 1 的吡啶基中性配体性质对配合物结构的影响，选择了五种中性配体（bipy = 4,4'-联吡啶；bpa = 1,2-双（4-吡啶基）乙烷；bpe = 1,2-双（4-吡啶基）乙烯；bpp = 1,3-双（4-吡啶基）丙烷；bpdap = N,N'-双（3-吡啶基）-2,6-二氨基吡啶），并合成了一系列新的银（I）二羧酸酯：{[Ag(bpa)(HADC)]}(n)（2），{[Ag(bpp)(HADC)].CH3OH}(n)（3），{[Ag(4)(bpe)(3)(ADC)(2)].2H2O}(n)（4），{[Ag(bipy)(HADC)].H2O}(n)（5），{[Ag(2)(bipy)(2)(ADC)].6H2O}(n)（6）和[Ag(8)(bpdap)(4)(ADC)(4)].2C2H5OH.6H2O（7）。单晶 X 射线结构分析表明，配合物 1 和 4 是由弱 Ag-Ag 相互作用的六核和四核 Ag（I）簇形成的。配合物 2 和 3 是双核结构，5 和 6 表现出无限的 1D 链状结构，而 7 是离散的八核 Ag（I）单元。1-7 的结构从双核、四核、六核到八核 Ag（I）配合物跨越，这表明次级配体在这种配位结构的形成中确实起着重要作用。还讨论了化合物的热稳定性、X 射线粉末衍射和发光性能。
