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手性(R,R)-1,2-环己二胺分别与具有偶数亚甲基烷烃链的S-M-1(4,4’-(butane-1,4-diylbis(oxy))-dibenzaldehyde),S-M-2(4,4’-(octane-1,8-diylbis(oxy))dibenzaldehyde)和S-M-3(4,4’-(dodecane-1,12-diylbis(oxy))-dibenzaldehyde)单元,通过亲核取代-消除反应合成相应的新颖柔性高分子P-1,P-2和P-3.Eu(TTA)3·2H2O分别与P-1,P-2和P-3反应制备相应的柔性稀土Eu(Ⅲ)高分子P-4,P-5和P-6.通过对烷烃主链数目的有效调控,能够有效调控稀土Eu(Ⅲ)的发光效率和圆偏振荧光的不对称因子(glum).实验证明,在一定的激发状态下,稀土高分子仅仅显示Eu(Ⅲ)的红色特征荧光,归于高分子将激发态能量基本传递给配位中心的Eu(Ⅲ)离子.通过对稀土Eu(Ⅲ)高分子的荧光寿命和量子效率表征,P-4,P-5和P-6的发光效率依次降低.P-4与P-5圆偏振荧光(CPL)的最大不对称因子(glum)分别为+0.0873和+0.0115,归属为电偶极跃迁(5D0→7F2);P-6最大不对称因子(glum)为+0.0539,归属为磁偶极跃迁(5D0→7F1).通过烷烃主链数目的差异实现对其CPL的有效调控,调控机理归于高分子折叠所引起稀土Eu(Ⅲ)不对称配位环境的变化.
Chiral (R, R) -1,2-cyclohexanediamine was reacted with SM-1 (4,4’-butane-1,4-diylbis (oxy)) - dibenzaldehyde with an even- SM-2 (4,4’- octane-1,8-diylbis (oxy)) dibenzaldehyde and SM-3 The corresponding novel flexible polymers P-1, P-2 and P-3.Eu (TTA) 3 · 2H2O were synthesized by nucleophilic substitution-elimination reaction and reacted with P-1, P-2 and P-3 respectively Of rare earth Eu (Ⅲ) polymers P-4, P-5 and P-6.The effective regulation of the number of alkane main chain can effectively control the luminescent efficiency and asymmetry factor of circularly polarized fluorescence (glum) .Experiments show that under certain excitation conditions, the rare earth polymer only shows the red characteristic fluorescence of Eu (Ⅲ) and belongs to the Eu (Ⅲ) ion whose energy is substantially transmitted by the polymer to the coordination center. The luminescence efficiency of P-4, P-5 and P-6 decreased with the increase of fluorescence lifetime and quantum efficiency of rare earth Eu (Ⅲ) polymer.The maximum asymmetry of P-4 and P-5 circularly polarized fluorescence (glum) were +0.0873 and +0.0115, respectively, belonging to the electric dipole transition (5D0 → 7F2); P-6 maximum asymmetry factor (glum) was +0.0539 Belongs to the magnetic dipole transition (5D0 → 7F1), and effectively regulates its CPL through the difference of the number of alkane main chains, and the regulation mechanism is attributed to the change of the asymmetric coordination environment of rare earth Eu (Ⅲ) caused by polymer folding.