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  本文關(guān)鍵詞： 有機(jī)金屬 非線性光學(xué) 釕化物 齊聚苯乙烯撐　出處：《江南大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

【摘要】：將富電子的金屬中心與齊聚苯乙烯撐(OPV)鏈段相連接形成具有中心對稱結(jié)構(gòu)的金屬炔基配合物被證明是很有發(fā)展前景的三階非線性光學(xué)材料。目前的研究工作多集中于對含有齊聚苯乙炔撐(OPE)單元的化合物的研究,所以本課題將合成一系列含有不同OPV共軛鏈長度的有機(jī)金屬化合物。隨著OPV共軛鏈的增長,化合物的溶解度會急劇下降,因此有必要在OPV共軛鏈苯環(huán)上引入烷氧基來增加其在有機(jī)溶劑中的溶解性。本論文主要研究共軛鏈長度對其三階非線性光學(xué)性能的影響。通過Horner-Wadsworth-Emmons、Sonogashira偶聯(lián)反應(yīng)以及脫甲硅基保護(hù)反應(yīng)合成得到了一系列不同共軛鏈長度的四種端炔化合物b1、b2、b3和b4。將這四種端炔化合物與cis-[RuCl(dppe)_2]PF_6金屬釕配體反應(yīng)生成含有不同OPV共軛鏈長度的有機(jī)金屬化合物: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)。對上述化合物主要采用核磁分析(1H-NMR、13C-NMR和31P-NMR)、全反射傅里葉紅外光譜(IR)、質(zhì)譜(HRMS)、元素分析進(jìn)行結(jié)構(gòu)與分子測定。通過紫外-可見吸收光譜(UV)、電化學(xué)(CV)、光譜電化學(xué)(UV-Vis-NIR)研究等手段對有機(jī)金屬化合物的光譜性質(zhì)進(jìn)行了表征。同時用Z-scan技術(shù)測試了其三階非線性光學(xué)性能,并且得到了非常大的雙光子和三光子吸收截面。結(jié)果表明隨著OPV共軛鏈的增長,其雙光子和三光子吸收最大值增加,但是在化合物達(dá)到含有8個對亞苯基亞乙炔基(PV)單元時,增加趨勢將不再明顯。這時候,通過增加OPV共軛鏈的長度將對化合物的多光子吸收最大值改變不明顯。
[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.

【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O627
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本文編號：1456872