2,2’-联吡啶衍生物为配体的磷光铼配合物的合成与性质分析

发布时间：2018-06-05 10:23

本文选题：吡啶 + 衍生物　；参考：《长春理工大学》2017年硕士论文

【摘要】：本论文设计合成了四个2,2'-联吡啶(dpy)衍生物配体:4,6,6'-三苯基-2,2'-联吡啶(L-1),6'-(2,4-二氟苯基)-4,6-二苯基-2,2'-联吡啶的合成(L-2),4-(4',6'-二苯基-[2,2'-联吡啶]-6-基)苯甲醛(L-3),9-(4-(4',6'-二苯基-[2,2'-联吡啶]-6-基)苯基)-9H-咔唑(L-4),并以L-1~L-4为配体合成了四个Re(I)配合物Re(CO)_3(L-1)Br(Re-1),Re(CO)_3(L-2)Br(Re-2),Re(CO)_3(L-3)Br(Re-3),Re(CO)_3(L-4)Br(Re-4)。研究了配体的光物理性质和配合物的聚集诱导发光、氧传感性质,同时,对配合物的基态几何结构和紫外-可见吸收光谱进行了理论模拟。本论文的主要研究内容如下:1.通过Claisen-Schmidt缩合反应、Kr?hnke合环反应、Suzuki偶联反应合成四种2,2'-联吡啶衍生物配体L-1~L-4。采用核磁共振氢谱、紫外-可见吸收光谱、荧光光谱,电化学等手段表征L-1~L-4的结构和性质。它们在THF溶液中和固体状态下的荧光光谱表明:配体的发射峰均在358~430nm之间,属于蓝紫光。电化学表明:配体L-3中引入的醛基使其EHOMO能级值相比较而言增大了0.2eV,而L-4中引入的咔唑基团使其ELUMO能级值相比较而言减小了0.62~0.69eV左右。2.以L-1~L-4为配体分别合成了四个Re(I)配合物Re-1~Re-4,这四个Re(I)配合物在THF溶液中的发射峰均在350nm处,为配体的π→π*跃迁发射,粉末状态下的常温以及低温发射峰均在580nm左右,为金属到配体的3MLCT跃迁发射。这些光谱表明Re-1~Re-4是属于聚集诱导磷光配合物。在THF/H2O的混合溶剂中,Re-1~Re-4的最大相对磷光量子效率值分别为1.16%(f_(H2O)=80%)、1.32%(f_(H2O)=96%)、0.33%(f_(H2O)=80%)和6.57%(f_(H2O)=80%)。3.分别通过DFT和TDDFT方法在b3lyp(lanl2dz+6-31g)水平下理论研究了Re-1~Re-4的基态几何形状和UV-Vis吸收光谱。研究发现,配合物Re-1~Re-3的前线分子轨道分布相似,Re-1~Re-4的LUMOs主要成分是配体中dpy的π*轨道,Re-1~Re-3的HOMOs主要由金属Re的d轨道,CO和Br的π轨道组成,而Re-4的HOMOs主要分布在咔唑基团的π轨道上,这可能是因为咔唑基团具有较强的给电子能力。
[Abstract]:In this paper, we have designed and synthesized four ligands of 2 ~ (2 +) -dipyridine-6-diphenyl-diphenylidene-6-benzaldehyde (L-3) -3-triphenylformaldehyde-6- [22diphenyl-dipyridyl] -6- (6-pyridyl) benzaldehyde 6- [22diphenyl-diphenylpyridyl] -6- (dipyridyl) -dipyridyl (2-diphenylpyridyl) -6-dipyridyl (6-dipyridyl) -dipyridyl. Four L-1~L-4 complexes were synthesized with L-1~L-4 as ligand. The complexes ReCoC ~ (3) L ~ (-1) ~ (?) ~ (3)? The photophysical properties of ligands and the aggregation induced luminescence and oxygen sensing properties of the complexes were studied. At the same time, the ground state geometry and UV-Vis absorption spectra of the complexes were theoretically simulated. The main contents of this thesis are as follows: 1. Four kinds of ligands, L-1 and L-4, were synthesized by Claisen-Schmidt condensation reaction. The structure and properties of L-1~L-4 were characterized by nuclear magnetic resonance (NMR), UV-Vis absorption spectra, fluorescence spectra and electrochemistry. The fluorescence spectra of the ligands in THF solution and in solid state show that the emission peaks of ligands are between 358~430nm and belong to blue violet light. The electrochemical results showed that the EHOMO energy level of L-3 increased by 0.2 EV compared with that of L-3, while the ELUMO energy level of L-4 decreased by 0.2 compared with that of L-4. Four Reo I) complexes were synthesized with L-1~L-4 as ligand respectively. The emission peaks of these four complexes in THF solution are at 350nm, which are 蟺 ~ + 蟺 * transition emission of ligands. The emission peaks at room temperature and low temperature in powder state are about 580nm. The emission is 3MLCT transition from metal to ligand. These spectra indicate that Re-1~Re-4 is a aggregation induced phosphorescence complex. The maximum relative phosphorescence quantum efficiency values of Re-1 / Re-4 in THF/H2O mixed solvent are 1.16 and 1.32 respectively. The maximum relative phosphorescence quantum efficiency is 1.16 in the mixed solvent of THF/H2O. The maximum relative phosphorescence quantum efficiency is 1.16. The maximum relative phosphorescence quantum efficiency is 1.16 and 1.32 respectively. The ground state geometry and UV-Vis absorption spectra of Re-1~Re-4 were studied by DFT and TDDFT methods at the b3lyp(lanl2dz 6-31 g level, respectively. It has been found that the main component of the LUMOs of the complex Re-1~Re-3 is the 蟺 * orbit of dpy in the ligand, and the HOMOs of the Re-1Re-3 is mainly composed of CO and 蟺 orbitals of Br and CO of the d orbitals of the metal re, the main component of the LUMOs is the 蟺 * orbit of dpy in the ligand, and the HOMOs of the complex is mainly composed of the d orbitals of the metal re. The HOMOs of Re-4 is mainly distributed in the 蟺 orbital of carbazole group, which may be due to the strong electron ability of carbazole group.
【学位授予单位】：长春理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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