新型三苯基氧膦类中性配体及其铕（Ⅲ）配合物的合成与性能研究
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摘要
本论文合成了一系列新型苯并氮杂环类中性配体,在三苯基氧磷的基础上引入苯并噁唑、苯并噻唑类基团,提高了配体的电子传输性,增大了配体的共轭程度,该系列中性配体对铕(Ⅲ)有很好的敏化发光作用。
配体Lx的结构：
利用五种芳香氮杂环膦氧类配体(L1-L5)为中性配体,分别以二苯甲酰甲烷(DBM)、α-噻吩甲酰三氟丙酮(TTA)、六氟乙酰丙酮(HFAC)、2-羟基-4-甲氧基二苯甲酮(BP)、硝酸根(N03-)为第一配体合成了五个系列共24种配合物,通过X-射线单晶衍射分析和元素分析对配合物的结构和组成进行了确证。通过测定配体的三线态能级、紫外吸收光谱、发光量子效率和寿命等性质,系统研究了系列发光配合物的光致发光性质。
结果表明：五种芳香杂环膦氧类配体与铕离子的激发三线态能级匹配较好,对中心离子均有较好的敏化发光作用。五个系列配合物在300～500nm范围的光线激发下均表现出较强的铕(Ⅲ)特征发射,其中以TTA系列配合物的光致发光效率最高,其量子效率最高可达36.4%,最有可能成为潜在的电致发光材料。配合物的光致发光性能优于以三苯基氧膦(TPPO)为中性配体的配合物,这说明新合成的中性配体是一类优良的敏化铕(Ⅲ)发光的配体。
One novel series of N-heterocyclic neutral ligands were synthesized. They were N-heterocyclic gropus modified triphenylphosphine oxide ligands, which were synthesized by introducing benzoxazole or benzothiazole moieties into the triphenylphosphine oxide framework. The resultant triphenylphosphine oxide derivatives have enlarged conjugation planes and improved rigidity and electronic transmission. They show good antennae effects for sensitizing Eu(III) emissions.
The structure of the ligand Lx:
Using five new N-heterocyclic gropus modified triphenylphosphine oxide derivatives as the neutral ligands and dibenzoylmethanate (DBM),2-thenoyltrifluoroacetonate (TTA), hexafluoroacetonate (HFAC),2-hydroxy-4-methoxybenzophenone (BP) and nitrate (NO3-) as the first ligands respectively, four series of total24new ternary europioum(III) complexes were synthesized. The photoluminescence properties of the complexes were thoroughly investigated through analyzing the triplet state energy levels of the neutral ligands, photoluminescent quantum yields and lifetimes.
The above results showed that:the triplet state energy levels of the neutral ligands match well with the5D0state of Eu3+ion and can efficiently sensitize the euripum(III) emissions. The five series solid complexes exhibit intense red emission of Eu(III) ion at room temperature under the excitation of300-500nm, of which the luminescent efficiencies of TTA series complexes are among the best with the highest quantum yield up to36.4%. It is most likely to become a potential red electroluminescent material. The complexes with triphenylphosphine oxide derivatives as neutral ligands show good luminescent properties than that with TPPO as neutral ligands, suggesting that newly synthesized neutral ligand is an excellent sensitizer for europium (Ⅲ) luminescence.
配体Lx的结构：
利用五种芳香氮杂环膦氧类配体(L1-L5)为中性配体,分别以二苯甲酰甲烷(DBM)、α-噻吩甲酰三氟丙酮(TTA)、六氟乙酰丙酮(HFAC)、2-羟基-4-甲氧基二苯甲酮(BP)、硝酸根(N03-)为第一配体合成了五个系列共24种配合物,通过X-射线单晶衍射分析和元素分析对配合物的结构和组成进行了确证。通过测定配体的三线态能级、紫外吸收光谱、发光量子效率和寿命等性质,系统研究了系列发光配合物的光致发光性质。
结果表明：五种芳香杂环膦氧类配体与铕离子的激发三线态能级匹配较好,对中心离子均有较好的敏化发光作用。五个系列配合物在300～500nm范围的光线激发下均表现出较强的铕(Ⅲ)特征发射,其中以TTA系列配合物的光致发光效率最高,其量子效率最高可达36.4%,最有可能成为潜在的电致发光材料。配合物的光致发光性能优于以三苯基氧膦(TPPO)为中性配体的配合物,这说明新合成的中性配体是一类优良的敏化铕(Ⅲ)发光的配体。
One novel series of N-heterocyclic neutral ligands were synthesized. They were N-heterocyclic gropus modified triphenylphosphine oxide ligands, which were synthesized by introducing benzoxazole or benzothiazole moieties into the triphenylphosphine oxide framework. The resultant triphenylphosphine oxide derivatives have enlarged conjugation planes and improved rigidity and electronic transmission. They show good antennae effects for sensitizing Eu(III) emissions.
The structure of the ligand Lx:
Using five new N-heterocyclic gropus modified triphenylphosphine oxide derivatives as the neutral ligands and dibenzoylmethanate (DBM),2-thenoyltrifluoroacetonate (TTA), hexafluoroacetonate (HFAC),2-hydroxy-4-methoxybenzophenone (BP) and nitrate (NO3-) as the first ligands respectively, four series of total24new ternary europioum(III) complexes were synthesized. The photoluminescence properties of the complexes were thoroughly investigated through analyzing the triplet state energy levels of the neutral ligands, photoluminescent quantum yields and lifetimes.
The above results showed that:the triplet state energy levels of the neutral ligands match well with the5D0state of Eu3+ion and can efficiently sensitize the euripum(III) emissions. The five series solid complexes exhibit intense red emission of Eu(III) ion at room temperature under the excitation of300-500nm, of which the luminescent efficiencies of TTA series complexes are among the best with the highest quantum yield up to36.4%. It is most likely to become a potential red electroluminescent material. The complexes with triphenylphosphine oxide derivatives as neutral ligands show good luminescent properties than that with TPPO as neutral ligands, suggesting that newly synthesized neutral ligand is an excellent sensitizer for europium (Ⅲ) luminescence.
引文
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