具有ICT性质的β-二酮及其金属有机配合物的光致发光性质研究
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摘要
我们设计合成了具有ICT(Intramolecular Charge Transfer,分子内电荷转移跃迁)性质的β-二酮NDBM、NDP及其铕(Ⅲ)和铱(Ⅲ)配合物,并分别对其光致发光性质进行了研究。为了对比,我们同时还合成并研究了DBM和NBM及其铕(Ⅲ)和铱(Ⅲ)配合物。
在研究Eu(NDBM)_3·3H_2O和Eu(NDP)_3·3H_2O体系时没有发现有电荷转移激发态参与的敏化稀土中心离子发光的过程,敏化中心离子是由三重态来完成的。我们研究的两个具有电荷转移激发态的分子NDBM和NDP的N原子上的电子容易分散到相邻的苯环上面,因此配体的能级较NBM和DBM有所降低。二甲氨基的引入使得NDBM和NDP的△E(~1ππ~*-~3ππ~*)太低,不利于系间窜越的发生,对提高Eu~(3+)荧光量子产率不利,故而Eu(NDBM)_3·3H_2O和Eu(NDP)_3·3H_2O的Eu~(3+)荧光量子产率很低;同时配体吸收的能量很大一部分被耗散在了CT荧光上。与Gd~(3+)和Eu~(3+)配位之后,NDBM和NDP的CT荧光量子产率显著降低。在溶液中,Eu(NDP)_3Phen·H_2O和Eu(NDBM)_3Phen的Eu~(3+)特征发射也很弱。在固体状态下,Eu(NDBM)_3·3H_2O和Eu(NDP)_3·3H_2O有很弱的Eu~(3+)的特征发射而没有配体的荧光了,Eu(NDBM)_3Phen也只有Eu~(3+)的特征发射,配体的荧光淬灭了。
为了研究辅助配体分子内电荷转移跃迁和不同能级对于红色磷光铱(Ⅲ)配合物光致发光性能的影响,我们合成了Ir(DBQ)_2(LX)(LX=acac,DBM,NDBM,NBM,NDP)这五种三价铱配合物。通过测试我们发现所用辅助配体的能级均高于Ir(DBQ)_2部分的三重态能级,所以配合物的最低自旋禁阻激发态主要来自于Ir(DBQ)_2部分。在常温除氧的CH_2Cl_2溶液中,Ir(DBQ)_2(LX)(LX=DBM,NDBM,NBM,NDP)与Ir(DBQ)_2(acac)在红光区的最大发射波长620 nm很接近,同属磷光发射,磷光量子产率随着它们的辅助配体与Ir(DBQ)_2部分的三重态能级之差的降低而降低。当配合物受到激发时,辅助配体吸收能量被激发到单重态,由于存在着以铱(Ⅲ)为中心的旋轨耦合作用,使得系间窜越几率大大增加,辅助配体的荧光量子产率大大降低,形成的辅助配体三重态把能量传递给Ir(DBQ)_2部分,这使得在低温条件下也观测不到其磷光发射。
In order to study on PL properties,severalβ-diketone with ICT function and corresponding Eu(Ⅲ),Ir(Ⅲ) complexes have been designed and synthesized. DBM,NBM and their Eu(Ⅲ),Ir(Ⅲ) complexes also been investigated to show contrast.
Photophysical studies demonstrated that no energy was migrated from the ICT excited state of the ligands to Eu~(3+),and that Eu~(3+) was sensitized by the triplet state. The triplet state energy level of NDBM and NDP decrease as the incorporation of the dimethylamino moiety into DBM and NBM respectively,which cause the conjugation system is enlarged.We concluded that the incorporation of the dimethylamino moiety affect the ISC of CDBM and further impaired the whole sensitization process. Quantum yields of Eu(NDBM)_3·3H_2O and Eu(NDP)_3·3H_2O are less than Eu(DBM)_3·2H_2O and Eu(NBM)_3·2H_2O.The ICT fluorescence quantum yields of NDBM and NDP decrease after coordinating with Gd~(3+) and Eu~(3+).In solution,the emission intensity of Eu~(3+) in Eu(NDP)_3Phen·H_2O and Eu(NDBM)_3Phen is still weak. There is no observable ligand emission in the solid state emission spectra in Eu(NDBM)_3Phen,Eu(NDBM)_3·3H_2O and Eu(NDP)_3·3H_2O,ICT fluorescence have been quenched in the solid state.
In order to investigate effect of ICT and energy levels of ancillary ligands on red phosphorescent Iridium(Ⅲ) complexes,we synthesize Ir(DBQ)_2(LX)(LX=acac, DBM,NDBM,NBM,NDP).For all of the complexes discussed thus far,the triplet levels of the ligands lie above the energies of the C^N ligand and MLCT excited states.Thus,the luminescence is dominated by C^N and MLCT transitions.In degassed CH_2Cl_2 solution at room temperature,theλ_(max)/nm(emmision) of Ir(DBQ)_2(LX)(LX=DBM,NDBM,NBM,NDP) is about 620 nm.Phosphorescent quantum yields decrease as the triplet energy level differences between Ir(DBQ)_2 andβ-diketone decrease.Strong spin-orbit coupling of the Ir(Ⅲ) leads to efficient intersystem crossing of the singlet excited states to the triplet manifold,so the ICT fluorescence quantum yields of ancillary ligands decrease drastically.The energy transfer from triplet excited states of ancillary ligands to triplet energy level of Ir(DBQ)_2.
在研究Eu(NDBM)_3·3H_2O和Eu(NDP)_3·3H_2O体系时没有发现有电荷转移激发态参与的敏化稀土中心离子发光的过程,敏化中心离子是由三重态来完成的。我们研究的两个具有电荷转移激发态的分子NDBM和NDP的N原子上的电子容易分散到相邻的苯环上面,因此配体的能级较NBM和DBM有所降低。二甲氨基的引入使得NDBM和NDP的△E(~1ππ~*-~3ππ~*)太低,不利于系间窜越的发生,对提高Eu~(3+)荧光量子产率不利,故而Eu(NDBM)_3·3H_2O和Eu(NDP)_3·3H_2O的Eu~(3+)荧光量子产率很低;同时配体吸收的能量很大一部分被耗散在了CT荧光上。与Gd~(3+)和Eu~(3+)配位之后,NDBM和NDP的CT荧光量子产率显著降低。在溶液中,Eu(NDP)_3Phen·H_2O和Eu(NDBM)_3Phen的Eu~(3+)特征发射也很弱。在固体状态下,Eu(NDBM)_3·3H_2O和Eu(NDP)_3·3H_2O有很弱的Eu~(3+)的特征发射而没有配体的荧光了,Eu(NDBM)_3Phen也只有Eu~(3+)的特征发射,配体的荧光淬灭了。
为了研究辅助配体分子内电荷转移跃迁和不同能级对于红色磷光铱(Ⅲ)配合物光致发光性能的影响,我们合成了Ir(DBQ)_2(LX)(LX=acac,DBM,NDBM,NBM,NDP)这五种三价铱配合物。通过测试我们发现所用辅助配体的能级均高于Ir(DBQ)_2部分的三重态能级,所以配合物的最低自旋禁阻激发态主要来自于Ir(DBQ)_2部分。在常温除氧的CH_2Cl_2溶液中,Ir(DBQ)_2(LX)(LX=DBM,NDBM,NBM,NDP)与Ir(DBQ)_2(acac)在红光区的最大发射波长620 nm很接近,同属磷光发射,磷光量子产率随着它们的辅助配体与Ir(DBQ)_2部分的三重态能级之差的降低而降低。当配合物受到激发时,辅助配体吸收能量被激发到单重态,由于存在着以铱(Ⅲ)为中心的旋轨耦合作用,使得系间窜越几率大大增加,辅助配体的荧光量子产率大大降低,形成的辅助配体三重态把能量传递给Ir(DBQ)_2部分,这使得在低温条件下也观测不到其磷光发射。
In order to study on PL properties,severalβ-diketone with ICT function and corresponding Eu(Ⅲ),Ir(Ⅲ) complexes have been designed and synthesized. DBM,NBM and their Eu(Ⅲ),Ir(Ⅲ) complexes also been investigated to show contrast.
Photophysical studies demonstrated that no energy was migrated from the ICT excited state of the ligands to Eu~(3+),and that Eu~(3+) was sensitized by the triplet state. The triplet state energy level of NDBM and NDP decrease as the incorporation of the dimethylamino moiety into DBM and NBM respectively,which cause the conjugation system is enlarged.We concluded that the incorporation of the dimethylamino moiety affect the ISC of CDBM and further impaired the whole sensitization process. Quantum yields of Eu(NDBM)_3·3H_2O and Eu(NDP)_3·3H_2O are less than Eu(DBM)_3·2H_2O and Eu(NBM)_3·2H_2O.The ICT fluorescence quantum yields of NDBM and NDP decrease after coordinating with Gd~(3+) and Eu~(3+).In solution,the emission intensity of Eu~(3+) in Eu(NDP)_3Phen·H_2O and Eu(NDBM)_3Phen is still weak. There is no observable ligand emission in the solid state emission spectra in Eu(NDBM)_3Phen,Eu(NDBM)_3·3H_2O and Eu(NDP)_3·3H_2O,ICT fluorescence have been quenched in the solid state.
In order to investigate effect of ICT and energy levels of ancillary ligands on red phosphorescent Iridium(Ⅲ) complexes,we synthesize Ir(DBQ)_2(LX)(LX=acac, DBM,NDBM,NBM,NDP).For all of the complexes discussed thus far,the triplet levels of the ligands lie above the energies of the C^N ligand and MLCT excited states.Thus,the luminescence is dominated by C^N and MLCT transitions.In degassed CH_2Cl_2 solution at room temperature,theλ_(max)/nm(emmision) of Ir(DBQ)_2(LX)(LX=DBM,NDBM,NBM,NDP) is about 620 nm.Phosphorescent quantum yields decrease as the triplet energy level differences between Ir(DBQ)_2 andβ-diketone decrease.Strong spin-orbit coupling of the Ir(Ⅲ) leads to efficient intersystem crossing of the singlet excited states to the triplet manifold,so the ICT fluorescence quantum yields of ancillary ligands decrease drastically.The energy transfer from triplet excited states of ancillary ligands to triplet energy level of Ir(DBQ)_2.
引文
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[1]J.P.Duan,P.P.Sun,C.H.Cheng.New Iridium Complexes as Highly Efficient Orange-Red Emitters in Organic Light-Emitting Diodes.Adv.Mater.,2003,15,224-228.
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[5]Z.W.Liu,M.Guan,Z.Q.Bian,et al.Red Phosphorescent Iridium Complex Containing Carbazole-Functionalized b-Diketonate for Highly Efficient Nondoped Organic Light-Emitting Diodes.Adv.Funct.Mater.,2006,16,1441-1448.
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[9]J.K.Yu,Y.M.Cheng,Y.H.Hu,et al.Probing Triplet State Properties of Organic Chromophores via Design and Synthesis of Os(Ⅱ)-Diketonate Complexes:The Triplet State Intramolecular Charge Transfer.J.Phys.Chem.B.,2004,108, 19908-19911.
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