螺旋结构双β-二酮稀土配合物的构筑及CPL性质研究

发布时间：2018-07-04 06:54

本文选题：手性 + 圆偏振荧光　；参考：《黑龙江大学》2016年硕士论文

【摘要】：本文设计并合成了四种新颖的双β-二酮配体:3,3-双(4,4,4-三氟-1,3-二氧代丁基)(2,5-二羟基-3,4-环氧基二环[2.2.0]呋喃)(HFBD),3,3-双(4,4,4-三氟-1,3-二氧代丁基)(2,2-联苯)(BBT),5,5-双(4,4,4-三氟-1,3-二氧代丁基)噻吩(DTT),5,5-双(4,4,4-三氟-1,3-二氧代丁基)(2,2-二联噻吩)(BTT)。通过引入不同的手性基团,配体与稀土离子以3:2比例的形成了四个手性螺旋结构的双β-二酮稀土配合物。其螺旋手性及相关的手性光学性质通过圆二色光谱和圆偏振荧光光谱等光谱技术进行了系统的研究,具体内容如下:1.通过引入手性间隔基的方式合成了手性双β-二酮配体3,3-双(4,4,4-三氟-1,3-二氧代丁基)(2,5-二羟基-3,4-环氧基二环[2.2.0]呋喃)(HFBD)。红外、紫外、核磁、质谱等一系列光谱表征证明配体与稀土离子以3:2的比例形成了双核手性稀土配合物Eu2(HFBD)3(H2O)4。配合物的光物理性质通过吸收光谱、圆二色光谱、发射光谱、圆偏振荧光光谱、荧光动力学衰减等光谱手段进行了研究。结果显示手性间隔基的引入诱导了β-二酮配体基态和激发态的光学活性,CD光谱显示出基于β-二酮单元的特征跃迁,而从CPL光谱中可以观察到铕离子的特征圆偏振荧光发射。2.通过在非手性双β-二酮稀土配合物中引入膦氧辅配体的方式合成了三个具有手性螺旋结构的稀土配合物:Eu2DTT3(BINAPO)2,Eu2(BBT)3(BINAPO)2和Eu2BTT3(BINAPO)2。通过红外、紫外、核磁、质谱等一系列表征证明了配体与稀土离子以3:2的比例形成了双核手性稀土配合物。对配合物的光物理性质进行了研究,得到了相应的吸收光谱、荧光发射光谱、圆二色光谱和圆偏振荧光光普以及荧光动力学衰减等光谱。结果显示手性膦氧辅配体的引入诱导了β-二酮配体基态和激发态的光学活性,CD光谱显示出基于β-二酮单元的特征跃迁,而从CPL光谱中可以观察到铕离子的特征圆偏振荧光发射。
[Abstract]:Four novel double beta - two ketone ligands were designed and synthesized: 3,3- double (4,4,4- three fluorine -1,3- two oxygen generation Ding Ji) (2,5- two hydroxyl -3,4- epoxy group [2.2.0] furan) (HFBD), 3,3- double (4,4,4- three fluorine -1,3- two) (2,2- biphenyl) (2,2- biphenyl) (BBT)), bilateral (three fluoride three fluorine two oxygen) thiophene (three fluorine two oxygen) Substituted Ding Ji (2,2- two thiophene) (BTT). By introducing different chiral groups, the ligand and rare-earth ions are formed by the proportion of rare earth ions to the four chiral double beta two ketone rare earth complexes. Their helical chirality and related chiral optical properties have been systematically studied by circular two color spectra and circular partial vibration fluorescence spectroscopy. The specific contents are as follows: 1. the chiral bis beta two ketone ligand 3,3- double (4,4,4- three fluoro -1,3- two oxygen generation Ding Ji) (2,5- two hydroxyl -3,4- epoxy 2 ring [2.2.0] furan) (HFBD) was synthesized by the introduction of chiral septum. The IR, UV, NMR and MS spectra showed that the ligand and rare-earth ions were formed by the ratio of rare earth ions to 3:2. The photophysical properties of the rare earth complex Eu2 (HFBD) 3 (H2O) 4. complex are studied by absorption spectra, circular two color spectra, emission spectra, circular polarization fluorescence, and fluorescence kinetic attenuation. The results show that the introduction of chiral spacers induces the optical activity of the base state and excited state of the beta two ketone ligand, and the CD spectrum shows the basis. The characteristic transition of the beta two ketone element is observed, and the characteristic circular polarization fluorescence emission (.2.) of the europium ions can be observed from the CPL spectrum. Three rare earth complexes with chiral helix structure are synthesized by the introduction of the phosphine oxygenate ligand in the rare earth's rare earth complexes: Eu2DTT3 (BINAPO) 2, Eu2 (BBT) 3 (BINAPO) 2 and Eu2BTT3 (BINAPO) 2. A series of characterizations such as infrared, UV, NMR, and MS have proved that the ligand and rare earth ions have formed a dual core chiral rare earth complex in the proportion of 3:2. The photophysical properties of the complexes are studied, and the corresponding absorption spectra, fluorescence emission spectra, circular two color spectra and circular polarized fluorescent photoluminescence, and the attenuation of fluorescence dynamics are obtained. The results show that the introduction of the chiral phosphine oxide ligand induces the optical activity of the base state and the excited state of the beta two ketone ligand. The CD spectrum shows the characteristic transition based on the beta two ketone unit, and the characteristic circular polarization fluorescence emission of the europium ions can be observed from the CPL spectrum.
【学位授予单位】：黑龙江大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

【相似文献】