Chen Yanli, Zhang Ying, Zhu Peihua, Fan Yingju, Bian Yongzhong, Li Xiyou, Jiang Jianzhuang
Key Lab for Colloid and Interface Chemistry of Education Ministry, Department of Chemistry, Shandong University, Jinan 250100, China.
J Colloid Interface Sci. 2006 Nov 1;303(1):256-63. doi: 10.1016/j.jcis.2006.07.043. Epub 2006 Jul 22.
A series of five carefully designed tris(phthalocyaninato) gadolinium triple-decker complexes [Pc(R)8]Gd[Pc(R')8]Gd[Pc(R'')8] (R=R'=R''=H; R=R'=H, R''=OC8H17; R=R''=H, R'=OC8H17; R=H, R'=R''=OC8H17; R=R'=R''=OC8H17) (1-5) were prepared and the film forming properties on water surface were systematically investigated. The limited mean molecular area obtained by pi-A isotherms revealed an "edge-on" conformation for all these compounds. UV-vis absorption spectra showed red-shifted Q bands, indicating the formation of J aggregates and effective intermolecular interaction in solid film. Phthalocyanine rings were found to take tilted orientation with respect to the normal of substrate according to the polarized absorption spectroscopic measurements. Low angle X-ray diffraction results provide direct evidence and therefore clearly clarify the point, for the first time, that unsymmetrical triple-decker molecules pack on the water surface with the unsubstituted phthalocyanine ring set close to the water surface and the substituted phthalocyanine ligand with octyloxy groups lies on the top.
制备了一系列五个精心设计的三（酞菁基）钆三层配合物[Pc(R)8]Gd[Pc(R')8]Gd[Pc(R'')8]（R=R'=R''=H；R=R'=H，R''=OC8H17；R=R''=H，R'=OC8H17；R=H，R'=R''=OC8H17；R=R'=R''=OC8H17）（1-5），并系统研究了它们在水面上的成膜性能。通过π-A等温线获得的有限平均分子面积表明所有这些化合物均呈“边缘立着”构象。紫外可见吸收光谱显示Q带红移，表明在固体薄膜中形成了J聚集体并存在有效的分子间相互作用。根据偏振吸收光谱测量结果，发现酞菁环相对于基底法线呈倾斜取向。低角度X射线衍射结果提供了直接证据，因此首次明确阐明了不对称三层分子在水面上的堆积方式，即未取代的酞菁环靠近水面，而带有辛氧基的取代酞菁配体位于顶部。
