含联吡啶，Eu(III)或Gd(III)的手性高分子配合物的合成及荧光性质研究

手性高分子P–1由(R)-5,5′-二溴-6,6′-二(4-三氟甲基苯基)-2,2′-二正辛氧基-1,1′-联萘(R–M–1)和5,5′-二乙烯基-2,2′-联吡啶(M–2)通过Pd催化的Heck偶合反应合成得到，高分子配合物P-2和P-3由高分子P-1与Eu(TTA)3·2H2O和Gd(TTA)3·2H2O (TTA– = 2-噻吩甲酰三氟丙酮)反应生成。手性高分子P-1能发射强的蓝色荧光，这是由于手性重复单元(R)-6,6′-二(4-三氟甲基苯基)-2,2′-二正辛氧基-1,1′-联萘和单元2,2′-联吡啶通过亚乙烯基桥连形成共轭高分子结构造成的。在不同的激发波长激发下，含Eu(III)的高分子配合物P–2不仅显示高分子荧光，还可显示Eu(III) (5D0→7F2)特征荧光。含Gd(III)的高分子配合物P–3仅发射高分子荧光。基于高分子及含RE(III)的高分子配合物的荧光性质研究发现，共轭高分子并没有把能量转移到Eu(III)或Gd(III) 配合物部分，只发射它自身的荧光，含Eu(III)的高分子配合物P–2发射Eu(III) (5D0→7F2)特征荧光能量主要来源于配阴离子TTA–。

Synthesis and Fluorescent Properties of Chiral Polymer Complexes Incorporating Bipyridine and Eu(III) or Gd(III)

Chiral polymer P‐1 was synthesized by the polymerization of (R)‐5,5′‐dibromo‐6,6'‐di(4‐trifluoromethyl‐ phenyl)‐2,2′‐bisoctoxy‐1,1'‐binaphthyl (R ‐M‐1 ) with 5,5′‐divinyl‐2,2′‐bipyridine ( M‐2 ) via Pd‐catalyzed Heck reaction. The polymer complexes P‐2 and P‐3 could be obtained by the bipyridyl coordination of P‐1 with Eu(TTA)₃·2H₂O and Gd(TTA)₃·2H₂O (TTA^?=1‐(2‐thenoyl)‐3,3,3‐trifluoroacetonate). The chiral polymer P‐1 shows strong blue fluorescence due to the extended ‐electronic structure between the chiral repeating unit (R)‐6,6'‐di(4‐trifluoromethyl‐phenyl)‐2,2′‐bisoctoxy‐1,1'‐binaphthyl and the conjugated linker 2,2′‐bipyridyl (bpy) group via vinylene bridge. The Eu(III)‐containing polymer complex P‐2 can not only emit the polymer fluorescence, but also have the characteristic fluorescence of Eu(III) (⁵D₀→⁷F₂) under different exciting wavelengths. The Gd(III)‐containing polymer complex P‐3 only emits the polymer fluorescence. Based on the fluorescent properties of the polymer and RE(III)‐containing polymer complexes, it can be concluded that the chiral polymer does not transfer energy to Eu(III) or Gd(III) complex moiety but emits its own fluorescence.