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主链中带有带电铱配合物的π共轭螯合聚合物:合成、表征、能量转移及电化学性质

pi-Conjugated chelating polymers with charged iridium complexes in the backbones: synthesis, characterization, energy transfer, and electrochemical properties.

作者信息

Liu Shu-Juan, Zhao Qiang, Chen Run-Feng, Deng Yun, Fan Qu-Li, Li Fu-You, Wang Lian-Hui, Huang Chun-Hui, Huang Wei

机构信息

Institute of Advanced Materials (IAM), Fudan University, 220 Handan Road, Shanghai 200433, China.

出版信息

Chemistry. 2006 May 24;12(16):4351-61. doi: 10.1002/chem.200501095.

Abstract

A series of pi-conjugated chelating polymers with charged iridium (Ir) complexes in the backbones were synthesized by a Suzuki polycondensation reaction, leading to homogeneous polymeric materials that phosphoresce red light. The fluorene and bipyridine (bpy) segments were used as polymer backbones. 5,5'-Dibromobipyridine served as a ligand to form a charged iridium complex monomer with 1-(9'9-dioctylfluorene-2-yl)isoquinoline (Fiq) as the cyclometalated ligand. Chemical and photophysical characterization confirmed that Ir complexes were incorporated into the backbones as one of the repeat units by means of the 5,5'-dibromobipyridine ligand. Chelating polymers showed almost complete energy transfer from the host fluorene segments to the guest Ir complexes in the solid state when the feed ratio was 2 mol %. In the films of the corresponding blend system, however, energy transfer was not complete even when the content of Ir complexes was as high as 16 mol %. Both intra- and intermolecular energy-transfer processes existed in this host-guest system, and the intramolecular energy transfer was a more efficient process. All chelating polymers displayed good thermal stability, redox reversibility, and film formation. These chelating polymers also showed more efficient energy transfer than the corresponding blended system and the mechanism of incorporation of the charged Ir complexes into the pi-conjugated polymer backbones efficiently avoided the intrinsic problems associated with the blend system, thus offering promise in optoelectronic applications.

摘要

通过铃木缩聚反应合成了一系列主链中带有带电铱(Ir)配合物的π共轭螯合聚合物,得到了发出红光磷光的均相聚合物材料。芴和联吡啶(bpy)片段用作聚合物主链。5,5'-二溴联吡啶用作配体,与1-(9'9-二辛基芴-2-基)异喹啉(Fiq)作为环金属化配体形成带电铱配合物单体。化学和光物理表征证实,Ir配合物通过5,5'-二溴联吡啶配体作为重复单元之一并入主链。当进料比为2 mol%时,螯合聚合物在固态下显示出从主体芴片段到客体Ir配合物几乎完全的能量转移。然而,在相应共混体系的薄膜中,即使Ir配合物的含量高达16 mol%,能量转移也不完全。在这种主客体体系中存在分子内和分子间的能量转移过程,且分子内能量转移是更有效的过程。所有螯合聚合物均表现出良好的热稳定性、氧化还原可逆性和成膜性。这些螯合聚合物还显示出比相应共混体系更有效的能量转移,并且将带电Ir配合物有效并入π共轭聚合物主链的机制有效避免了与共混体系相关的固有问题,因此在光电应用中具有前景。

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