含OPV链段的钌炔基化合物的合成及其三阶非线性光学性质的研究

发布时间：2018-01-23 05:53

  本文关键词： 有机金属 非线性光学 钌化物 齐聚苯乙烯撑　出处：《江南大学》2016年硕士论文　论文类型：学位论文

【摘要】：将富电子的金属中心与齐聚苯乙烯撑(OPV)链段相连接形成具有中心对称结构的金属炔基配合物被证明是很有发展前景的三阶非线性光学材料。目前的研究工作多集中于对含有齐聚苯乙炔撑(OPE)单元的化合物的研究,所以本课题将合成一系列含有不同OPV共轭链长度的有机金属化合物。随着OPV共轭链的增长,化合物的溶解度会急剧下降,因此有必要在OPV共轭链苯环上引入烷氧基来增加其在有机溶剂中的溶解性。本论文主要研究共轭链长度对其三阶非线性光学性能的影响。通过Horner-Wadsworth-Emmons、Sonogashira偶联反应以及脱甲硅基保护反应合成得到了一系列不同共轭链长度的四种端炔化合物b1、b2、b3和b4。将这四种端炔化合物与cis-[RuCl(dppe)_2]PF_6金属钌配体反应生成含有不同OPV共轭链长度的有机金属化合物:trans-[RuCl(dppe)_2]{C≡C-1-C_6H_4-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-C H=CH-1-C_6H_4-4-C≡C}-trans-[RuCl(dppe)_2](c1)、trans-[RuCl(dppe)_2]{C≡C-1-C_6H_4-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}2-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-CH=CH-1-C_6H_4-4-C≡C}-trans-[RuCl(dppe)_2](c2)、trans-[RuCl(dppe)_2]{C≡C-1-C_6H_4-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}2-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}2-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-CH=CH-1-C_6H_4-4-C≡C}-trans-[RuCl(dppe)_2](c3)、trans-[RuCl(dppe)_2]{C≡C-1-C_6H_4-4-(E)-CH=CH-1-C_6H_4-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}2-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}2-4-(E)-C H=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-CH=CH-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-CH=C H-1-C_6H_2-{2,5-O(CH_2)_5CH_3}_2-4-(E)-CH=CH-1-C_6H_4-4-(E)-CH=CH-1-C_6H_4-4-C≡C}-trans-[RuCl(dppe)_2](c4)。对上述化合物主要采用核磁分析(1H-NMR、13C-NMR和31P-NMR)、全反射傅里叶红外光谱(IR)、质谱(HRMS)、元素分析进行结构与分子测定。通过紫外-可见吸收光谱(UV)、电化学(CV)、光谱电化学(UV-Vis-NIR)研究等手段对有机金属化合物的光谱性质进行了表征。同时用Z-scan技术测试了其三阶非线性光学性能,并且得到了非常大的双光子和三光子吸收截面。结果表明随着OPV共轭链的增长,其双光子和三光子吸收最大值增加,但是在化合物达到含有8个对亚苯基亚乙炔基(PV)单元时,增加趋势将不再明显。这时候,通过增加OPV共轭链的长度将对化合物的多光子吸收最大值改变不明显。
[Abstract]:The metal rich electron and homogeneous polystyrene support (OPV) segments are connected to form a metal acetylide complexes with centrosymmetric structure proved to be three order nonlinear optical material with good prospect of development. The current research work mainly focus on containing oligo phenylene ethynylene (OPE) of the unit compound. So this topic will synthesize a series of OPV with different conjugation lengths of organometallic compounds with OPV. The increase of conjugated chains, the solubility of a compound will be a sharp decline, so it is necessary to introduce the alkoxy chain in OPV conjugate benzene ring to increase its solubility in organic solvents. This paper mainly studies on effect of conjugated chain length the third-order NLO properties. Through Horner-Wadsworth-Emmons, Sonogashira coupling reaction and desilylation protection reaction synthesized four kinds of terminal alkynes with a series of different conjugate chain length Compound B1, B2, B3 and b4. of the four terminal alkyne compounds with cis-[RuCl (DPPE) _2]PF_6 metal ruthenium ligand reaction of organometallic compounds containing different OPV conjugated chain length: trans-[RuCl (DPPE) _2]{C = C-1-C_6H_4-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3} _2-4- (E) -C H=CH-1-C_6H_4-4-C = C}-trans-[RuCl (DPPE) _2] (C1), trans-[RuCl (DPPE) _2]{C = C-1-C_6H_4-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}_2-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}2-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}_2-4- (E) -CH=CH-1-C_6H_4-4-C = C}-trans-[RuCl (DPPE) _2] (C2), trans-[RuCl (DPPE) _2]{C = C-1-C_6H_4-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}2-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}2-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}_2-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}_2-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2 _5CH_3}_2-4-) (E) -CH=CH-1-C_6H_4-4-C = C}-trans-[RuCl (DPPE) _2] (C3), trans-[RuCl (DPPE) _2]{C = C-1-C_6H_4-4- (E) -CH=CH-1-C_6H_4-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}2-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}2-4- (E) -C H=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}_2-4- (E) -CH=CH-1-C_6H_2-{2,5-O (CH_2) _5CH_3}_2-4- (E) -CH=C H-1-C_6H_2-{2,5-O (CH_2) _5CH_3}_2-4- (E) -CH=CH-1-C_6H_4-4- (E) -CH=CH-1-C_6H_4-4-C = C}-trans-[RuCl (DPPE) _2] (C4). Of these compounds mainly by NMR analysis (1H-NMR, 13C-NMR and 31P-NMR), total reflection Fourier transform infrared spectroscopy (IR), mass spectrometry (HRMS), elemental analysis and molecular structure determination by UV. The visible absorption spectra (UV), electrochemical (CV), spectroelectrochemistry (UV-Vis-NIR) on the spectral properties of metal organic compounds were characterized by Z-scan technology. At the same time tested Third order nonlinear optical properties, and has very large two-photon and three photon absorption cross section. The results show that OPV with the increase of conjugated chains, the two photon and three photon absorption maximum value increased, but reached 8 containing p-phenylene ethynylene compounds (PV) in a single element, will no longer increase trend obvious. At this time, by increasing the length of the chain will be OPV conjugate compounds on multiphoton absorption maximum change is not obvious.

【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O627
，

本文编号：1456872