發(fā)布時(shí)間：2018-06-05 10:23

  本文選題：吡啶 + 衍生物　； 參考：《長春理工大學(xué)》2017年碩士論文

【摘要】：本論文設(shè)計(jì)合成了四個(gè)2,2'-聯(lián)吡啶(dpy)衍生物配體:4,6,6'-三苯基-2,2'-聯(lián)吡啶(L-1),6'-(2,4-二氟苯基)-4,6-二苯基-2,2'-聯(lián)吡啶的合成(L-2),4-(4',6'-二苯基-[2,2'-聯(lián)吡啶]-6-基)苯甲醛(L-3),9-(4-(4',6'-二苯基-[2,2'-聯(lián)吡啶]-6-基)苯基)-9H-咔唑(L-4),并以L-1~L-4為配體合成了四個(gè)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)。研究了配體的光物理性質(zhì)和配合物的聚集誘導(dǎo)發(fā)光、氧傳感性質(zhì),同時(shí),對配合物的基態(tài)幾何結(jié)構(gòu)和紫外-可見吸收光譜進(jìn)行了理論模擬。本論文的主要研究內(nèi)容如下:1.通過Claisen-Schmidt縮合反應(yīng)、Kr?hnke合環(huán)反應(yīng)、Suzuki偶聯(lián)反應(yīng)合成四種2,2'-聯(lián)吡啶衍生物配體L-1~L-4。采用核磁共振氫譜、紫外-可見吸收光譜、熒光光譜,電化學(xué)等手段表征L-1~L-4的結(jié)構(gòu)和性質(zhì)。它們在THF溶液中和固體狀態(tài)下的熒光光譜表明:配體的發(fā)射峰均在358~430nm之間,屬于藍(lán)紫光。電化學(xué)表明:配體L-3中引入的醛基使其EHOMO能級值相比較而言增大了0.2eV,而L-4中引入的咔唑基團(tuán)使其ELUMO能級值相比較而言減小了0.62~0.69eV左右。2.以L-1~L-4為配體分別合成了四個(gè)Re(I)配合物Re-1~Re-4,這四個(gè)Re(I)配合物在THF溶液中的發(fā)射峰均在350nm處,為配體的π→π*躍遷發(fā)射,粉末狀態(tài)下的常溫以及低溫發(fā)射峰均在580nm左右,為金屬到配體的3MLCT躍遷發(fā)射。這些光譜表明Re-1~Re-4是屬于聚集誘導(dǎo)磷光配合物。在THF/H2O的混合溶劑中,Re-1~Re-4的最大相對磷光量子效率值分別為1.16%(f_(H2O)=80%)、1.32%(f_(H2O)=96%)、0.33%(f_(H2O)=80%)和6.57%(f_(H2O)=80%)。3.分別通過DFT和TDDFT方法在b3lyp(lanl2dz+6-31g)水平下理論研究了Re-1~Re-4的基態(tài)幾何形狀和UV-Vis吸收光譜。研究發(fā)現(xiàn),配合物Re-1~Re-3的前線分子軌道分布相似,Re-1~Re-4的LUMOs主要成分是配體中dpy的π*軌道,Re-1~Re-3的HOMOs主要由金屬Re的d軌道,CO和Br的π軌道組成,而Re-4的HOMOs主要分布在咔唑基團(tuán)的π軌道上,這可能是因?yàn)檫沁蚧鶊F(tuán)具有較強(qiáng)的給電子能力。
[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.
【學(xué)位授予單位】：長春理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 陳玉璽;;永久性氚發(fā)光涂料[J];涂料工業(yè);1990年05期

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本文編號：1981651