發(fā)布時間：2018-04-13 13:05

  本文選題：咔唑 + 咪唑��； 參考：《山東師范大學(xué)》2017年碩士論文

【摘要】：金屬-有機(jī)框架是由金屬為連接點(diǎn),有機(jī)物為linker的超分子配位聚合物,具有多孔性。本文以咔唑?yàn)槟阁w合成了一系列含氮雜環(huán)的彎折型剛性有機(jī)配體,研究了其與過渡金屬的自組裝的合成方法和結(jié)構(gòu)調(diào)控規(guī)律,得到了8例配位化合物,通過X-射線單晶衍射、元素分析和紅外等測試表征了它們的結(jié)構(gòu),并研究了部分化合物的功能化性質(zhì)。Ⅰ.通過溶劑熱法,利用以2,7-二溴咔唑?yàn)槟阁w的有機(jī)配體L1、L2和L3分別與過渡金屬Cd(Ⅱ)反應(yīng),組裝得到3例結(jié)構(gòu)穩(wěn)定的配位化合物(化合物1、化合物2和化合物3),通過元素分析、紅外、X-射線粉末衍射、熱重分析和X-射線單晶衍射等手段表征了它們的結(jié)構(gòu),并研究了取代基對調(diào)控結(jié)構(gòu)的影響。Ⅱ.利用以咔唑?yàn)槟阁w,咪唑?yàn)槎嘶�有機(jī)配體L2、L3、L4和L5分別與Ni(OAc)_2·4H_2O通過溶劑熱反應(yīng)自組裝得到4例未見文獻(xiàn)報(bào)道的二維金屬-有機(jī)框架(化合物4、化合物5、化合物6和化合物7)。該四例化合物同構(gòu)且具有良好的電催化性質(zhì),它們分別與GC電極形成的復(fù)合電極材料在電催化水解產(chǎn)氧性質(zhì)上有一定的效果。選取在中性緩沖液中電催化性能較好的化合物4,研究其在不同p H緩沖液下的電催化性能,可以發(fā)現(xiàn)化合物4在p H=6的緩沖液中有較好的電催化性能,并且可以持續(xù)利用長達(dá)18小時。Ⅲ.利用已合成的有機(jī)配體L2和苯二甲酸混配與Mn Cl_2·4H_2O在溶劑熱條件下組裝得到一例分子結(jié)構(gòu)的配位化合物[Mn(C_(20)H_(17)N_5)_2(H_2O)_4]·2(C_8H_5O_4)·2(H_2O),該化合物是以二價錳金屬為配位中心的六配位結(jié)構(gòu),參與配位的兩個氮原子分別來自于兩個有機(jī)配體L2的咪唑端基,四個氧原子來配位的水分子。弱的相互作用力在形成三維結(jié)構(gòu)中有不可或缺的作用,其三維結(jié)構(gòu)是分子是通過三種π-π作用和七種氫鍵形成的。同時,我們也對其熱失重分析進(jìn)行了表征。
[Abstract]:Metal-organic framework is a supramolecular coordination polymer with metal as junction point and organic matter as linker.A series of flexural rigid organic ligands containing nitrogen heterocycles were synthesized using carbazole as the parent. The synthesis method and structural regulation of the complexes with transition metals were studied. Eight coordination compounds were obtained by X-ray single crystal diffraction.Their structures were characterized by elemental analysis and IR, and the functionalized properties of some compounds were studied.Three structurally stable coordination compounds (compound 1, compound 2 and compound 3) were synthesized by solvothermal reaction with transition metal Cd2 and L3, respectively, using the organic ligands L1, L2 and L3, which were based on 2-dibromocarbazole, and were analyzed by elemental analysis.Their structures were characterized by infrared X-ray powder diffraction, thermogravimetric analysis and X-ray single crystal diffraction, and the effects of substituents on their regulatory structures were studied.Using carbazole as parent, imidazole as terminal organic ligand L _ 2N _ 3L _ 3L _ 4 and L _ 5 as terminal organic ligands, respectively, by solvothermal self-assembly with Ni(OAc)_2 4H_2O, four unreported two-dimensional metal-organic frameworks (compound 4, compound 5, compound 6 and compound 7) were obtained.The four compounds are isomorphic and have good electrocatalytic properties. The composite electrode materials formed with GC electrode have certain effect in electrocatalytic hydrolysis of oxygen.The electrocatalytic activity of compound 4 in neutral buffer solution was studied. It was found that compound 4 had better electrocatalytic activity in buffer solution of pH 6.And can be used for up to 18 hours.The two nitrogen atoms involved in the coordination come from the imidazole terminal group of two organic ligands L2 and the water molecules coordinated by four oxygen atoms.Weak interaction forces play an indispensable role in the formation of three-dimensional structures, which are formed by three kinds of 蟺-蟺 interaction and seven hydrogen bonds.At the same time, we also characterized the thermogravimetric analysis.
【學(xué)位授予單位】：山東師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4
，

本文編號：1744617