Liu Bing, Qian Dong-Jin, Huang Hong-Xiang, Wakayama Tatsuki, Hara Shigeki, Huang Wei, Nakamura Chikashi, Miyake Jun
Institute of Advanced Materials, Fudan University, Handan Road 200433, Shanghai, China.
Langmuir. 2005 May 24;21(11):5079-84. doi: 10.1021/la050064t.
On the basis of the coordination geometry of metal ions, regular cubic, clubbed, and wirelike nanocrystals of Cd(2+)-/PtCl(6)(2-)-mediated, and Hg(2+)-/Ag(+)-/PtCl(4)(2-)-mediated multiporphyrin arrays have been grown at the water-chloroform interface. The nanocrystal growth process was monitored by the transmission electron microscopy (TEM), which revealed (1) an intrinsic rule for coordination polymers, that is, the geometries of metal ions (as connects for the coordination polymers) dominate the frameworks of the related polymeric nanocrystals, and (2) one kind of intuitive nanocrystal growth processes at the interfaces. Both electron diffraction and X-ray diffraction patterns indicated the formation of well-defined nanocrystals. It was found that single-/microcrystals were formed at first, and then they grew into polycrystals. The nanocrystal layer was transferred onto Si and quartz substrate surfaces by the Langmuir-Blodgett method, with its composition analyzed by X-ray photoelectron spectroscopy as well as the arrangement of porphyrin macrocycles in the nanocrystals by UV-vis absorption spectroscopy.
基于金属离子的配位几何结构,在水-氯仿界面生长出了由Cd(2+)/PtCl(6)(2-)介导以及Hg(2+)/Ag(+)/PtCl(4)(2-)介导的规则立方体形、棒状和线状的多卟啉阵列纳米晶体。通过透射电子显微镜(TEM)监测纳米晶体的生长过程,结果表明:(1)配位聚合物存在一条内在规律,即金属离子的几何结构(作为配位聚合物的连接点)决定了相关聚合物纳米晶体的框架结构;(2)在界面处存在一种直观的纳米晶体生长过程。电子衍射和X射线衍射图谱均表明形成了结构明确的纳米晶体。研究发现,首先形成单晶/微晶,然后生长为多晶。通过朗缪尔-布洛杰特方法将纳米晶体层转移到硅和石英衬底表面,利用X射线光电子能谱分析其组成,并通过紫外-可见吸收光谱分析纳米晶体中卟啉大环的排列情况。