Matsumoto Wako, Naito Muneyuki, Danjo Hiroshi
Graduate School of Natural Science, Konan University 8-9-1 Okamoto, Higashinada Kobe 658-8501 Japan.
Department of Chemistry, Konan University 8-9-1 Okamoto, Higashinada Kobe 658-8501 Japan
RSC Adv. 2023 Aug 23;13(36):25002-25006. doi: 10.1039/d3ra03940d. eCollection 2023 Aug 21.
The immobilization of functional metal complexes onto polymer supports remains one of the most important research areas. In this study, we prepared spiroborate supramolecular and peapod polymers containing a cationic photoluminescent ruthenium(ii) complex. The supramolecular polymer was obtained by mixing spiroborate cyclic trimer bearing homoallyl group and a ruthenium(ii) tris(bipyridyl) complex, and was further converted into the corresponding peapod polymer by olefin metathesis polymerization. The structure of these polymers was determined by H NMR, dynamic light scattering, inductively coupled plasma-atomic emission spectroscopy, energy dispersive X-ray analyses, and atomic force microscopy. The absorption and emission behaviors of the ruthenium(ii) complex were almost the same for the free form and the supramolecular polymer in the mixed solvent of ,-dimethylformamide and chloroform, although the emission intensity decreased when the chloroform portion was increased. On the other hand, the hypsochromism was observed upon the emission of the ruthenium(ii) complex in the peapod polymer, probably due to the rigidochromic effect of the tight encapsulation by the peapod structure.
将功能性金属配合物固定在聚合物载体上仍然是最重要的研究领域之一。在本研究中，我们制备了含有阳离子光致发光钌（II）配合物的螺硼酸酯超分子聚合物和豆荚状聚合物。超分子聚合物通过将带有高烯丙基的螺硼酸酯环状三聚体与钌（II）三（联吡啶）配合物混合得到，并通过烯烃复分解聚合进一步转化为相应的豆荚状聚合物。这些聚合物的结构通过核磁共振氢谱、动态光散射、电感耦合等离子体原子发射光谱、能量色散X射线分析和原子力显微镜确定。在N，N-二甲基甲酰胺和氯仿的混合溶剂中，钌（II）配合物的游离形式和超分子聚合物的吸收和发射行为几乎相同，尽管当氯仿比例增加时发射强度降低。另一方面，在豆荚状聚合物中，钌（II）配合物发射时观察到蓝移现象，这可能是由于豆荚状结构紧密包封的刚性变色效应所致。
