本文選題：金屬釕化合物　切入點(diǎn)：光譜電化學(xué)　出處：《華中師范大學(xué)》2016年碩士論文

【摘要】：近年來(lái),隨著人們對(duì)電子產(chǎn)品微型化的需要,它們期望電子產(chǎn)品的尺寸能更小,因此科學(xué)家開(kāi)始了尋求合適材料的旅程,研究過(guò)程中分子導(dǎo)線吸引了它們的注意,因?yàn)榉肿訉?dǎo)線有尺寸小,多樣化,性能可調(diào)節(jié)等諸多優(yōu)點(diǎn),可以解決電子器件尺寸微型化的需要。分子導(dǎo)線可以通過(guò)合理的構(gòu)建來(lái)實(shí)現(xiàn),可是對(duì)于設(shè)計(jì)出的分子是否適合作為潛在的分子導(dǎo)線,科學(xué)家還需要進(jìn)行進(jìn)一步的驗(yàn)證,這就需要一些科學(xué)的手段和方法,而傳統(tǒng)的研究方法主要有電化學(xué)法,通常是使用電信號(hào)做為激勵(lì)和檢測(cè)手段,獲得的是電化學(xué)體系中各種微觀信息的總和,因此很難直觀、準(zhǔn)確地反映出電極和溶液界面間的各種反應(yīng)過(guò)程,反應(yīng)過(guò)程中的中間態(tài)的濃度,形態(tài)變化等,因此這給判斷電子傳輸機(jī)理帶來(lái)很大的問(wèn)題。光譜電化學(xué)技術(shù)于60年代初期由美國(guó)電化學(xué)家Adams, R. N提出,1964年由kuwana, T.實(shí)現(xiàn)。近60多年來(lái),光譜電化學(xué)得到了迅速發(fā)展,已經(jīng)成為電化學(xué)領(lǐng)域中一個(gè)重要的學(xué)科分支。目前,它已發(fā)展了多種檢測(cè)方法,紅外光譜電化學(xué),紫外-可見(jiàn)-近紅外光譜電化學(xué)等,對(duì)于分子導(dǎo)線的研究越來(lái)越重要。因此在本論文中我們主要是通過(guò)光譜電化學(xué)及理論計(jì)算等實(shí)驗(yàn)技術(shù)對(duì)不同取代的苯基以及低聚乙烯基橋聯(lián)的雙金屬釕化合物的性質(zhì)進(jìn)行研究,來(lái)進(jìn)一步探索其電子傳遞能力以及機(jī)理,判斷其作為分子導(dǎo)線的潛質(zhì)。具體的研究工作如下：1.對(duì)不同取代的苯基橋聯(lián)的雙核釕(Ⅱ)乙烯基化合物2-1-2-4進(jìn)行了電化學(xué)(循環(huán)伏安法及方波伏安法)、紅外光譜電化學(xué)、紫外-可見(jiàn)-近紅外光譜電化學(xué)及理論計(jì)算的研究,發(fā)現(xiàn)化合物2-1-2-4雖然有較大的半波電位分離,但2-1-2-4中兩個(gè)金屬釕之間沒(méi)有明顯的電子耦合,它們氧化到正一價(jià)時(shí)是基于橋配體的定域氧化。2.利用紅外光譜電化學(xué)、紫外-可見(jiàn)-近紅外光譜電化學(xué)和理論計(jì)算等技術(shù)對(duì)低聚乙烯基橋聯(lián)的雙核釕(Ⅱ)化合物3-1-3-4的電子性質(zhì)和電子轉(zhuǎn)移機(jī)制進(jìn)行了系統(tǒng)和深入地探索。所有的實(shí)驗(yàn)結(jié)果表明,兩個(gè)金屬釕之間電子耦合作用較弱。結(jié)合DFT理論研究,我們發(fā)現(xiàn)從3-1到3-4,隨著多烯鏈的延長(zhǎng),橋配體在氧化過(guò)程中的參與程度越來(lái)越大。
[Abstract]:In recent years, with the need for miniaturization of electronic products, they expect electronic products to be smaller in size, so scientists have embarked on a journey to find suitable materials, and molecular conductors have attracted their attention in the process. Because molecular conductors have many advantages, such as small size, diversification, adjustable performance and so on, they can solve the need of miniaturization of electronic devices. However, scientists still need to further verify whether the designed molecules are suitable for potential molecular conductors. This requires some scientific means and methods, and the traditional research methods are mainly electrochemical methods. Electrical signals are usually used as a means of excitation and detection to obtain the sum of all kinds of micro information in electrochemical system, so it is difficult to directly and accurately reflect all kinds of reaction processes between electrode and solution interface. Concentration of intermediate state, change of form, etc., in the process of reaction, In the early 1960s, spectroelectrochemistry was proposed by the American electrochemists AdamsR.N and realized in 1964 by Kuwana, T.Spectral Electrochemistry has developed rapidly in the last 60 years. It has become an important branch of the field of electrochemistry. At present, it has developed a variety of detection methods, such as infrared spectroscopy electrochemistry, UV-Vis near-infrared spectroscopy electrochemistry, etc. The study of molecular conductors is becoming more and more important. Therefore, in this thesis, we mainly study the properties of different substituted phenyl and poly (vinyl) -bridged bimetallic ruthenium compounds by means of spectroelectrochemistry and theoretical calculation. To further explore its electron transport capabilities and mechanisms, The specific research work is as follows: 1.Electrochemistry (cyclic voltammetry, square wave voltammetry, infrared spectroscopy) of binuclear ruthenium (鈪，

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