Synthesis And Properties Of Corrole Molecular Conductors

Energy is a topic of great concern today,with the depletion of traditional fossil fuels on the one hand and the more efficient access to clean energy on the other.Now we have many ways to obtain a variety of clean energy,the use of these energy is mostly in the form of electric energy,and the efficient use of electric energy depends on the carrier materials we use.The research background of this article is based on the current electronic components challenges,in microelectronics technology rapid development,now the integrated circuit density is more and more big,especially the emergence of very large scale integrated circuit,makes the element size smaller and smaller and lower power consumption,solid-state electronics theory and its processing technology are faced with enormous challenges.At the limits of size,devices and circuits operate with severe distortion due to the predominance of quantum statistical effects,with the diffusion of electronic wave functions to adjacent components.Therefore,as the micron technology has gradually reached its limit,nano electronic devices and molecular devices have emerged.In this paper,based on the research direction of molecular wire,the metal-molecular-metal(MMM)molecular junction was constructed to study the conductivity properties of organic single molecule.In the selection of organic molecules,this topic chose corrole this porphyrin derivative to study its single molecular conductivity properties,through the previous research,we can know that porphyrin is a very good conductive property of conjugated large ring structure molecules.However,no single molecule conductivity studies related to corrole have been published before,and all the molecules tested in this paper were synthesized and characterized in the laboratory,and then using the method of STM-BJ test(metal)corrole molecular single molecular conductive properties.The purpose of this paper is to design different configurations of(metal)corrole molecules,test their single molecular conductivity properties,explore the mechanism of electrical conductivity,to provide a reference for the research of molecular conductor materials.The main research contents are as follows:(1):Three A₂B sulfur-containing corrole free bases were designed and synthesized.Sulphur-containing substituents were selected at position 5 and 15 of corrole for testing purposes.According to the literature reviewed,the sulfur-containing substituents exposed at both ends of the conjugated skeleton could combine with the gold electrode more stably to form a molecular junction.The electron transport of the molecule is regulated by the use of substituents with different electron-absorbing abilities at position 10 of the corrole molecule.Before testing the conductivity properties of single molecules,the chemical compounds were characterized by means of NMR,UV and mass spectrometry,and the electrochemical CV and DPV of corrole molecules were tested to preliminarily understand the electronic structure of the compound molecules.(2):On the basis of(1),the 10-position substituent group was adjusted,and three corresponding A₂B metal cobalt corroles were synthesized.Before this,we also tested A₂B copper corrole complexes,and found that there was no significant breakthrough in the conductive properties of copper as the metal center.According to the research completed by the laboratory,the metal cobalt was selected as the center metal in this paper,not only because cobalt is a transition metal that can better regulate the electronic structure of corrole molecules,but also because cobalt has cheap and easy economic applicability.After doing the related characterization,the monomolecular conductance of cobalt corrole was tested.(3):After the completion of the single molecule conductivity test of the free base molecule of corrole and the metal cobalt corrole molecule,this paper changed the molecular structure design,and instead of changing the substituent group at position 10 of the corrole molecule,the substituent group at position 5 and 15 was adjusted.Asymmetric synthesis of a series of bromine and phenyl corrole a precursor for the coupling 4-methylthiophenyl of A₂B type cobalt metal sulfur(?)corrole molecules and bromine and phenyl corrole a precursor for the coupling thiophene(3-thiophene,2-thiophene)of A₂B type cobalt metal sulfur(?)corrole molecules.When the coupling group is 4-methylthiophenyl,a benzene ring is extended on both sides of the corrole molecule,which can explore the influence of the change of the length of the conductivity path and the change of the molecular configuration on the conductivity.When the coupling group is thiophene group,the conduction path of the corrole molecule may change.Therefore,by comparing the corrole molecule with the coupling group of 4-methylthiophenyl,the influence of different conduction path and different bonding on the single molecule charge transport can be explored,for thiophene groups,that is,3-thiophene or 2-thiophene,the effect of location isomerism on single-molecule charge transport can be explored.