Incorporation of fluorene groups into the salicylidene moiety significantly enhances the luminescence of a number of multinuclear alkynylated Zn(II)-salophen complexes. Preparation of these complexes was achieved by a synthetic strategy with facile handling of the reactants, simple purification of the products, and one-pot reaction process. Two synthetic methods are used for the preparation of different types of multinuclear salophen complexes. The introduction of a bis- or a tris-salicylaldehyde as a bridging unit in the presence of various alkynyl substituted monoimines in the reaction mixture containing zinc acetate resulted in the preparation of di- and tri-nuclear Zn(II)-salophen complexes of type 1, respectively. For a different type, treatment of tetraminobenzene with various arylethynyl-substituted salicylaldehyde afforded dinuclear Zn(II) alkynylated salophen complexes of type 2 with a different structure. The photophysical behaviors of these multinuclear metal salophen complexes were investigated. Particularly, the dinuclear complex 9b of type 1 having ethynylfluorene groups in salophen moieties and dialkoxyl groups in the bridging moiety exhibits higher quantum efficiency than that of other complexes in this report. In addition, the bis-Zn(II) alkynylated salophen complex 11e bearing nitrogen donor groups displays more red-shifted pattern than those with other functional substituents both in absorption and emission spectra.
在
水杨基中加入
芴基团可显著增强一些多核炔化 Zn(II)-salophen 复合物的发光性能。这些配合物的制备采用了反应物处理简便、产物纯化简单、一锅反应的合成策略。制备不同类型的多核盐
酚络合物采用了两种合成方法。在含有
醋酸锌的反应混合物中,引入双
水杨醛或三
水杨醛作为桥接单元,并加入各种炔基取代的单
亚胺,可分别制备出类型 1 的二核 Zn(II)-salophen 复合物和三核 Zn(II)-salophen 复合物。至于另一种类型,用各种芳基
乙炔基取代的
水杨醛处理四
氨基苯,可得到结构不同的 2 型双核 Zn(II) 烷炔化
水杨
酚配合物。研究了这些多核
金属丹
酚配合物的光物理行为。特别是在丹
酚分子中含有
乙炔基
芴基团、桥接分子中含有二羰基的 1 型双核配合物 9b 比其他配合物具有更高的量子效率。此外,含有氮供体基团的双
锌(II)炔化盐基络合物 11e 在吸收光谱和发射光谱中都比含有其他功能取代基团的络合物显示出更多的红移模式。