University of California, Santa Cruz, Department of Chemistry, 1156 High Street, Santa Cruz, CA 95064, USA.
Dalton Trans. 2010 Dec 14;39(46):11193-200. doi: 10.1039/c0dt01064b. Epub 2010 Oct 22.
We have successfully synthesized three cadmium-based metal-organic frameworks by utilizing two separate organic linkers to direct the structure. The first material is a three-dimensional neutral framework based on 2D cadmium ethanedisulfonate layers pillared by a 4,4'-bipyridine linker. The other two materials are 3D cationic frameworks and are the first with propanedisulfonate and butanedisulfonate as extraframework charge balancing anions. Both structures occupy a high symmetry hexagonal crystal system where Cd-bipy chains are arranged into three crystallographically distinct layers that stack spirally along [001]. The framework is stabilized by alkanesulfonate anions that are electrostatically and hydrogen bonded to the framework. Each material was characterized by single-crystal and powder X-ray diffraction. The thermal and luminescent properties were also investigated by thermogravimetric analysis and photoluminescence spectroscopy, respectively. All three materials exhibit high thermal stability to above 300 °C and efficient blue emissive photoluminescence centered at 425 nm to 450 nm upon 350 nm excitation.
我们成功地合成了三种基于镉的金属有机骨架，利用两种不同的有机配体来指导结构。第一种材料是一种基于二维镉乙二磺酸盐层的三维中性骨架，由 4,4'-联吡啶配体柱支撑。另外两种材料是三维阳离子骨架，是第一个以丙二磺酸盐和丁二磺酸盐作为额外的框架电荷平衡阴离子的骨架。这两种结构都占据了高对称的六方晶体系统，其中 Cd-bipy 链排列成三个在 [001] 方向上螺旋堆叠的结晶学上不同的层。骨架由烷烃磺酸盐阴离子稳定，这些阴离子通过静电和氢键与骨架相互作用。每种材料都通过单晶和粉末 X 射线衍射进行了表征。通过热重分析和荧光光谱分别研究了它们的热稳定性和发光性能。所有三种材料都表现出超过 300°C 的高热稳定性和在 350nm 激发下在 425nm 至 450nm 处的高效蓝色发射荧光。
