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引用次数: 0
摘要
电子通过π共轭分子的隧穿电导可能会受到分子轨道结构中存在的不同路径的影响,从而导致分子波函数的建设性或破坏性干涉。这种量子干涉(QI)直接转化为电导的增强或抑制,为通过定制合成来控制这种现象提供了可能。因此,我们建立了合成方法,以获得一系列硫原子位置明确的噻吩融合螺旋烯,从而控制导电、线性共轭以及中断、交叉共轭途径的出现。我们描述了这些合成策略,并将通过分子的预期电子传输与三个关键变量联系起来:a) 环内 S 原子的外/内拓扑结构;b) 符合螺旋烯的环总数的奇偶性(奇数/偶数);以及 c) 电路的大小。该系列包括从 [7] 到 [11] 的融合环,具有外向、内向或混合外向内向拓扑结构。通过比较具有尺寸可调的最高占位分子轨道(HOMO)/最低未占位分子轨道(LUMO)能量的同源二硫杂庚烯,我们可以将键拓扑结构这一关键变量从其他电子特性中分离出来,从而研究螺旋共轭分子中的 QI。了解和调整此类分子螺线管中的电导是这项研究的主要目的。
Design and synthesis of thiahelicenes for molecular electronics.
The conductance of a tunneling electron through a π-conjugated molecule may be affected by the presence of different pathways in the orbital structure of the molecule, resulting in the constructive or destructive interference of the molecular wave function. This quantum interference (QI) directly translates into enhancement or suppression of conductance and offers the possibility of controlling this phenomenon through tailored synthesis. Hence, we set up synthetic methodologies to access a series of thiophene-fused helicenes with a well-defined positioning of the sulfur atoms, which control the occurrence of conducting, linearly conjugated as well as disrupted, cross-conjugated pathways. We describe these synthetic strategies and relate the expected electronic transport through our molecules to three key variables: a) the exo-/endo-topology of the S atom within the ring; b) the parity (odd/even) of the overall number of rings conforming to the helicene; and c) the size of the circuit. This series ranks from [7] to [11] fused rings, having both exo-, endo-, or mixed exo-endo-topology. Comparison of homologous dithiahelicenes with size-tunable highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energies allows us to isolate the key variable of the bond topology from other electronic properties and face the study of QI in helically conjugated molecules. Understanding and tuning the conductance in such molecular solenoids is the main purpose of this work.
期刊介绍:
Frontiers in Chemistry is a high visiblity and quality journal, publishing rigorously peer-reviewed research across the chemical sciences. Field Chief Editor Steve Suib at the University of Connecticut is supported by an outstanding Editorial Board of international researchers. This multidisciplinary open-access journal is at the forefront of disseminating and communicating scientific knowledge and impactful discoveries to academics, industry leaders and the public worldwide.
Chemistry is a branch of science that is linked to all other main fields of research. The omnipresence of Chemistry is apparent in our everyday lives from the electronic devices that we all use to communicate, to foods we eat, to our health and well-being, to the different forms of energy that we use. While there are many subtopics and specialties of Chemistry, the fundamental link in all these areas is how atoms, ions, and molecules come together and come apart in what some have come to call the “dance of life”.
All specialty sections of Frontiers in Chemistry are open-access with the goal of publishing outstanding research publications, review articles, commentaries, and ideas about various aspects of Chemistry. The past forms of publication often have specific subdisciplines, most commonly of analytical, inorganic, organic and physical chemistries, but these days those lines and boxes are quite blurry and the silos of those disciplines appear to be eroding. Chemistry is important to both fundamental and applied areas of research and manufacturing, and indeed the outlines of academic versus industrial research are also often artificial. Collaborative research across all specialty areas of Chemistry is highly encouraged and supported as we move forward. These are exciting times and the field of Chemistry is an important and significant contributor to our collective knowledge.