本文選題：TTF + TTFV類衍生物　； 參考：《鄭州大學(xué)》2017年碩士論文

【摘要】：插烯類四硫富瓦烯(tetrathiafulvalene vinylogues,TTFV)由于其具有良好的供電子特性和顯著的結(jié)構(gòu)特征,在有機(jī)及無機(jī)材料方面引起了廣泛關(guān)注和研究。本文以噻吩醛、萘醛、以及含吡啶、冠醚基團(tuán)的1,3-二硫環(huán)戊烯為原料合成了七種新的TTFV類衍生物,并用1H NMR、13C NMR、FT-IR和ESI-MS進(jìn)行了結(jié)構(gòu)表征;同時(shí),通過循環(huán)伏安(cyclic voltammetry,CV),紫外-可見光譜(UV-Vis)和熒光光譜(Fluorescence spectrum)滴定等方法初步研究了TTFV類衍生物與金屬離子之間的相互作用。本論文主要包括以下幾個(gè)方面:1、綜述了TTF和TTFV衍生物的研究進(jìn)展。簡單介紹了四硫富瓦烯(tetrathiafulvalene,TTF)、TTFV衍生物的合成、結(jié)構(gòu)、性質(zhì)及其在超分子化學(xué)和材料化學(xué)等方面的應(yīng)用進(jìn)展。2、通過偶合成烯、氧化二聚等步驟合成了七種TTFV衍生物,并通過單晶X-射線衍射對(duì)其結(jié)構(gòu)進(jìn)行了確定。結(jié)合量子化學(xué)計(jì)算,分析了取代基對(duì)TTFV電化學(xué)行為的影響。使用親核試劑(碘甲烷,3-氯丙腈)和鋅鹽(I))為起始原料合成了含簡單功能基的硫酮化合物IV和V;(碘代吡啶,3,4-二碘苯并15-5醚(II),3,4-二碘苯并18-6醚(III)和鋅鹽(I)合成了化合物VI,VII和VIII,然后化合物IV,V,VI,VII和VIII在亞磷酸三甲酯存在下,分別與噻吩醛或萘醛發(fā)生烯化反應(yīng)生成二硫富瓦烯(dithiafulvalene,DTF)衍生物(DTF 1,DTF 2,DTF 3,DTF 4,DTF 5,DTF 6和DTF 7)。最后DTF衍生物通過I2氧化二聚生成TTFV衍生物(TTFV 1,TTFV 2,TTFV 3,TTFV 4,TTFV 5,TTFV 6和TTFV 7)。所有新化合物都通過了1H NMR、13C NMR、FT-IR和ESI-MS結(jié)構(gòu)表征。其中化合物(DTF 1,DTF 3,DTF 4,DTF 5,DTF 6,TTFV 1,TTFV 3和TTFV 4)又通過單晶X-射線衍射分析對(duì)其結(jié)構(gòu)進(jìn)行了確定。同時(shí),利用Gaussian 03程序包,采用含時(shí)密度泛函理論在B3LPY/6-31G*組水平上對(duì)化合物TTFV 1,TTFV 3和TTFV 4進(jìn)行理論計(jì)算。結(jié)果表明:HOMO軌道能量依次為TTFV 3TTFV 1TTFV 4,LUMO軌道能量仍然是TTFV 3TTFV 1TTFV 4。3、通過循環(huán)伏安、紫外滴定和熒光滴定等方法初步研究了目標(biāo)化合物與金屬離子之間的作用行為。通過循環(huán)伏安法(CV)和紫外滴定對(duì)目標(biāo)化合物(TTFV 3和TTFV 4)的電化學(xué)行為進(jìn)行了研究。結(jié)果表明,當(dāng)加入Cu2+、Al3+、Fe2+、Hg2+、Cd2+、Pb2+、Zn2+、Ag+和Fe3+離子時(shí),僅Hg2+、Cu2+、Fe3+和Ag+離子表現(xiàn)出較強(qiáng)的電化學(xué)識(shí)別行為。紫外滴定對(duì)化合物TTFV 3和TTFV 4研究表明,隨著加入Cu2+、Hg2+、Fe3+量的增加,紫外吸收光譜藍(lán)移20 nm,并在650 nm處出現(xiàn)新峰。熒光滴定顯示Fe3+和Hg2+有猝滅現(xiàn)象,其猝滅程度分別為50%和46%。
[Abstract]:Tetrathiafulvalene vinylogues (TTFV) has attracted extensive attention in organic and inorganic materials due to its good electronic properties and obvious structural characteristics. In this paper, seven new TTFV derivatives were synthesized from thiophene aldehyde, naphthaldehyde, and 1,3-dithiocyclopentene containing pyridine and crown ether group, and characterized by 1H NMR13C NMRFT-IR and ESI-MS. The interaction between TTFV derivatives and metal ions was studied by cyclic voltammetric cyclic voltammetry, UV-Vis-UV and fluorescence spectra titration. This paper mainly includes the following aspects: 1, and summarizes the research progress of TTF and TTFV derivatives. The synthesis, structure, properties and applications in supramolecular chemistry and material chemistry of tetrathiafulvaleneum derivatives were briefly introduced. Seven kinds of TTFV derivatives were synthesized by the steps of dimerization and dimerization. The structure was determined by single crystal X-ray diffraction. The influence of substituents on the electrochemical behavior of TTFV was analyzed by quantum chemistry calculation. Using nucleophilic reagents (iodomethane 3-chloropropionitrile) and zinc salt Ion as starting materials, thione compounds IV and VN containing simple functional groups were synthesized by synthesis of thione compounds IV and VN (iodipyridine-3-diiodobenzo 15-5 ether) and zinc salt iodide (鈪，

本文編號(hào)：1927573