Dppz配体10,13-位由芳香基取代的新型单核钌配合物的合成

目的 本论文以1，10-邻菲罗啉（1，10-phenanthroline，phen）为辅助配体，在主配体联吡啶类（3，2-a：2'-3'-c）吩嗪pyrido-（3，2-a：2'，3'-c）phenazine，dppz]的10，13-位分别引入噻吩、苯并噻吩、呋喃及苯并呋喃，设计并合成出对应4种新型单核二-（1，10-邻菲罗啉）-吡啶类（3，2-a：2'-3'-c）吩嗪合钌（Ⅱ）衍生物。方法 首先通过Suzuki偶联反应得到4种苯并噻二唑中间体，然后经CoCl₂催化、NaBH₄还原得到邻苯二胺类化合物，再经缩合反应得到对应的目标配合物。结果 苯并噻二唑中间体及对应的4种目标配合物通过磁共振氢谱、碳谱及高分辨质谱表征，紫外-可见吸收光谱进一步验证了目标配合物结构的正确性。结论 本论文通过多步反应合成出以1，10-邻菲罗啉为辅助配体，主配体dppz的10，13-位分别含有噻吩、苯并噻吩、呋喃及苯并呋喃的4种新型单核多吡啶钌配合物。紫外-可见吸收光谱实验表明尽管4种芳香取代基结构有差异，对应苯并噻二唑中间体和钌配合物的吸收光谱相似。

Synthesis of novel mononuclear Ru(Ⅱ) complexes with 10,13-diaryl substituents on the dppz ligands

Objective Four new ruthenium complexes with 1,10-phenanthroline ancillary ligand and 10, 13-position substitutedpyrido-(3,2-a:2',3'-c)phenazine,dppz] major ligands including thiophenyl,furanyl,2-benzo(b)thienyl]-2,1,3-benzothiadiazole and2-benzo(b)furanyl]-2,1,3-benzothiadiazole will be designed and synthesized. Methods Target complexes were made by condensation reaction of ruthenium complex with the appropriate 3,6-diaryl substituted benzene-1,2-diamine. The latter 3,6-diaryl substituted benzene-1,2-diamine was obtained by a Suzuki-coupling reaction, and subsequently by reduction with NaBH₄ under catalysis of CoCl₂. Results Benzothiadiazole intermediates and corresponding target complexes are well characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR and TOF-Mass. UV-vis absorption spectra of all ruthenium complexes further verify the structures of the target complexes. Conclusion In this paper, we have synthesized four mononuclear ruthenium complexes with 1,10-phenanthroline ancillary ligand and 10, 13-diaryl including thiophenyl,furanyl,2-benzo(b)thienyl]-2,1,3-benzothiadiazole and2-benzo(b)furanyl]-2,1,3-benzothiadiazole, substituted dppz as major ligand through multiple steps. Both four 4,7-position substituted 2,1,3-benzothiadiazole intermediates and corresponding ruthenium complexes exhibit substantially similar absorption spectra despite the structural difference.