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将硝基苯甲酸配基(NBA)键合在聚苯乙烯侧链,制得了硝基苯甲酸功能化的聚苯乙烯(PS-NBA),在此基础上使大分子配体PS-NBA与Eu(III)离子配位,制备了二元高分子-稀土配合物PS-(NBA)3-Eu(III),也以邻菲罗啉(Phen)为小分子配体,制备了三元高分子-稀土配合物PS-(NBA)3-Eu(III)-Phen1,重点研究了芳环上硝基取代基对高分子-稀土配合物光致发光性能的影响.研究结果表明,芳环上的硝基取代基对以Eu(III)为中心离子的苯甲酸功能化聚苯乙烯-稀土配合物的发光性能具有双重影响.硝基取代基通过配基内的电荷转移(ILCT),耗损配基激发单线态的能量,有效降低苯甲酸配基的三线态能量,使配基NBA最低三线态能级与Eu(III)离子共振能级之间的匹配程度显著增强,对Eu(III)离子的荧光发射发生强敏化作用,使配合物PS-(NBA)3-Eu(III)以及PS-(NBA)3-Eu(III)-Phen1产生了高强度的荧光发射,显现出硝基取代基对配合物发光性能的正性影响.另一方面,即使在稀溶液中,随着高分子-稀土配合物浓度从4.0×10-6mol·L-1增大至4.0×10-4mol·L-1,配合物的荧光发射也会逐渐变弱,这是由激发态的配合物向硝基发生荧光共振能量转移(FRET)的淬灭作用所导致的,表现出硝基取代基对配合物发光性能的负性影响.
Nitrobenzoate ligand (NBA) was bonded to polystyrene side chains to prepare nitrobenzoic acid-functionalized polystyrene (PS-NBA), on the basis of which the macromolecular ligand PS-NBA and (NBA) 3-Eu (III), which is a binary macromolecule-rare earth complex, has also been prepared by the coordination of Eu (III) Rare Earth Complex PS- (NBA) 3-Eu (III) -Phen1, we focused on the influence of nitro substituents on the photoluminescence properties of polymer-rare earth complexes. The results show that on the aromatic ring Had a dual effect on the luminescent properties of the benzoic acid-functionalized polystyrene-rare earth complexes with Eu (III) as the central ion. The nitro group was affected by charge transfer (ILCT) Excited the energy of singlet state, effectively reduced the triplet energy of benzoic acid ligand, and significantly enhanced the match between the lowest triplet energy level of the ligand and the Eu (III) ion resonance energy. The Eu (III) ions (NBA) 3-Eu (III) and PS- (NBA) 3-Eu (III) -Phen1 produced strong fluorescence emission, showing the nitro substitution Base to match On the other hand, with the polymer-rare earth complex concentration increasing from 4.0 × 10-6mol·L-1 to 4.0 × 10-4mol·L-1 even in dilute solution, The fluorescence emission of the complex will also be weakened, which is caused by the quenching effect of the excited state complex on the fluorescence of the nitro group by the resonance energy transfer (FRET), which shows that the nitro group substituent Negative impact.