不同取代的苯基以及低聚乙烯基桥联的双金属钌配合物的性质研究

发布时间：2018-03-24 17:46

  本文选题：金属钌化合物　切入点：光谱电化学　出处：《华中师范大学》2016年硕士论文

【摘要】：近年来,随着人们对电子产品微型化的需要,它们期望电子产品的尺寸能更小,因此科学家开始了寻求合适材料的旅程,研究过程中分子导线吸引了它们的注意,因为分子导线有尺寸小,多样化,性能可调节等诸多优点,可以解决电子器件尺寸微型化的需要。分子导线可以通过合理的构建来实现,可是对于设计出的分子是否适合作为潜在的分子导线,科学家还需要进行进一步的验证,这就需要一些科学的手段和方法,而传统的研究方法主要有电化学法,通常是使用电信号做为激励和检测手段,获得的是电化学体系中各种微观信息的总和,因此很难直观、准确地反映出电极和溶液界面间的各种反应过程,反应过程中的中间态的浓度,形态变化等,因此这给判断电子传输机理带来很大的问题。光谱电化学技术于60年代初期由美国电化学家Adams, R. N提出,1964年由kuwana, T.实现。近60多年来,光谱电化学得到了迅速发展,已经成为电化学领域中一个重要的学科分支。目前,它已发展了多种检测方法,红外光谱电化学,紫外-可见-近红外光谱电化学等,对于分子导线的研究越来越重要。因此在本论文中我们主要是通过光谱电化学及理论计算等实验技术对不同取代的苯基以及低聚乙烯基桥联的双金属钌化合物的性质进行研究,来进一步探索其电子传递能力以及机理,判断其作为分子导线的潜质。具体的研究工作如下：1.对不同取代的苯基桥联的双核钌(Ⅱ)乙烯基化合物2-1-2-4进行了电化学(循环伏安法及方波伏安法)、红外光谱电化学、紫外-可见-近红外光谱电化学及理论计算的研究,发现化合物2-1-2-4虽然有较大的半波电位分离,但2-1-2-4中两个金属钌之间没有明显的电子耦合,它们氧化到正一价时是基于桥配体的定域氧化。2.利用红外光谱电化学、紫外-可见-近红外光谱电化学和理论计算等技术对低聚乙烯基桥联的双核钌(Ⅱ)化合物3-1-3-4的电子性质和电子转移机制进行了系统和深入地探索。所有的实验结果表明,两个金属钌之间电子耦合作用较弱。结合DFT理论研究,我们发现从3-1到3-4,随着多烯链的延长,桥配体在氧化过程中的参与程度越来越大。
[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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