Chen Yanli, Liu Hong-Guo, Zhu Peihua, Zhang Ying, Wang Xueying, Li Xiyou, Jiang Jianzhuang
Key Lab for Colloid and Interface Chemistry of Education Ministry, Department of Chemistry, Shandong University, Jinan 250100, China.
Langmuir. 2005 Nov 22;21(24):11289-95. doi: 10.1021/la051796o.
Three heteroleptic tris(phathlocyaninato) dysprosium triple-decker complexes with different alkoxy groups at the peripheral positions of the medium phthalocyanine ligand (Pc)Dy[Pc(OCnH(2n+1))8]Dy(Pc) (n = 4, 8, 16) (I-III) {Pc = unsubstituted phthalocyaninate; Pc(OC4H9)8 = 2,3,9,10,16,17,23,24-octakis(butyloxy)phthalocyaninate; Pc(OC8H17)8 = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninate; Pc(OC16H33)8 = 2,3,9,10,16,17,23,24-octakis(hexadecyloxy)phthalocyaninate} have been synthesized, and their aggregate behaviors in monolayer and multilayer solid films have been comparatively studied. The pure compounds and their 1:4 mixtures with stearic acid (SA) have been found to form a stable monolayer at the air/water interface with a tilted edge-on orientation of (Pc)Dy[Pc(OCnH(2n+1))8]Dy(Pc) molecules. In the pure monolayers of the three triple-decker compounds, wirelike molecular aggregates were observed by high-resolution transmission electron microscopy (HRTEM). Adding SA has been found to prevent triple-decker compounds (Pc)Dy[Pc(OC4H9)8]Dy(Pc) (I) and (Pc)Dy[Pc(OC8H17)8]Dy(Pc) (II) from forming large aggregates, and small domains with a diameter of ca. 10 nm were observed in the mixed monolayers. HRTEM studies revealed that two crystalline phases with rectangular and hexagonal lattice structure are present in the small domains. However, both pi-A isotherms and HRTEM studies indicated that the mixed monolayer of compound (Pc)Dy[Pc(OC16H33)8]Dy(Pc) (III) with SA did not show a difference from the corresponding pure monolayer. The SA molecules were pressed into the cavity above the phthalocyanine ring formed by the eight long hexadecyloxy side chains of the medium macrocycle ligand in III. The multilayer LB films of all of these triple deckers fabricated by the vertical dipping method showed very good layered structure as revealed by the multiple-order diffraction peaks in low-angle X-ray diffraction (LAXRD) patterns.
合成了三种异质三（酞菁基）镝夹心配合物（Pc）Dy[Pc(OCnH(2n+1))8]Dy(Pc)（n = 4, 8, 16）（I - III），其中间酞菁配体（Pc）外围具有不同的烷氧基{ Pc = 未取代的酞菁；Pc(OC4H9)8 = 2,3,9,10,16,17,23,24 - 八（丁氧基）酞菁；Pc(OC8H17)8 = 2,3,9,10,16,17,23,24 - 八（辛氧基）酞菁；Pc(OC16H33)8 = 2,3,9,10,16,17,23,24 - 八（十六烷氧基）酞菁}，并对它们在单层和多层固体薄膜中的聚集行为进行了比较研究。发现纯化合物及其与硬脂酸（SA）的1:4混合物在空气/水界面形成稳定的单层，（Pc）Dy[Pc(OCnH(2n+1))8]Dy(Pc)分子呈倾斜的边缘取向。在三种夹心化合物的纯单层中，通过高分辨率透射电子显微镜（HRTEM）观察到丝状分子聚集体。发现添加SA可防止夹心化合物（Pc）Dy[Pc(OC4H9)8]Dy(Pc)（I）和（Pc）Dy[Pc(OC8H17)8]Dy(Pc)（II）形成大的聚集体，在混合单层中观察到直径约为10 nm的小区域。HRTEM研究表明，小区域中存在具有矩形和六边形晶格结构的两个晶相。然而，π - A等温线和HRTEM研究均表明，化合物（Pc）Dy[Pc(OC16H33)8]Dy(Pc)（III）与SA的混合单层与相应的纯单层没有差异。在III中，SA分子被压入由中间大环配体的八个长十六烷氧基侧链形成的酞菁环上方的空腔中。通过垂直浸渍法制备的所有这些夹心化合物的多层LB膜，如低角度X射线衍射（LAXRD）图谱中的多阶衍射峰所示，显示出非常好的层状结构。
