Building large-scale unimolecular scaffolding for electronic devices
Building large-scale unimolecular scaffolding for electronic devices
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DOI：
10.1016/j.mtchem.2022.101067
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发表时间：
2022-08-02
影响因子：
7.3
通讯作者：
Martin, S.
中科院分区：
文献类型：
--
作者：
Escorihuela, E.;Concellon, A.;Martin, S.
基于分子组件和材料的下一代（光）电子器件的制造将需要仔细的化学设计，以及允许器件结构内功能分子精确空间定向和排列的组装方法。尽管单分子电子学已经成为实验室现实，但分子连接内的分子排列在测量之间的变化是相当大的。因此，控制分子-金属接触处的精确几何形状是一个长期存在且很大程度上尚未解决的挑战。在这里，报道了一种制造以规则模式分布的均匀单分子连接的策略。单层锌金属卟啉，通过庞大的树突进行外围功能化，用于提供具有精确空间分布的明确的分子结合位点阵列。然后树枝通过光化学交联形成坚固的基层。随后通过逐层 (LbL) 策略在这些结合位点上组装平行、均匀间隔的单分子结构。这种 LbL 策略通过 cva-氨基官能化低聚（亚苯基）亚乙炔基 (OPE) 分子与金属卟啉模板基础层的锌离子的配位来进行。然后，该结构通过（交联的）锌卟啉和 OPE 的交替自组装层延伸。锌 (II) 位点和双功能 OPE 线之间的配位相互作用确保了层之间的高度对准以及通过扩展阵列的良好电接触，并提供对化学成分的精细控制。 (C) 2022 作者。由爱思唯尔有限公司出版
The fabrication of a future generation of (opto)electronic devices based on molecular components and materials will require careful chemical design, coupled with assembly methods that permit precise spatial orientation and arrangement of the functional molecules within device structures. Although unimolecular electronics are already a laboratory reality, the variation in the arrangement of the molecule within a molecular junction from measurement to measurement is considerable. Consequently, controlling the precise geometry at the molecule-metal contacts is a long-standing and largely unresolved challenge. Here, a strategy to fabricate uniform unimolecular junctions distributed in a regular pattern is reported. A monolayer of zinc metalloporphyrins, peripherally functionalised by bulky dendrons, is used to provide a well-defined array of molecular binding sites with precise spatial distribution. The dendrons are then photochemically cross-linked to form a robust base-layer. Parallel, uniformly-spaced unimolecular structures are subsequently assembled on these binding sites through a layer-by-layer (LbL) strategy. This LbL strategy proceeds through coordination of an cva-amino functionalised oligo(phenylene)ethynylene (OPE) molecule to the zinc ions of the metalloporphyrin template base-layer. The structure is then extended through alternating self-assembled layers of (cross-linked) zinc porphyrin and OPE. The coordination interaction between the zinc(II) sites and the bifunctional OPE wire ensures a high degree of registry between the layers and good electrical contact through the extended arrays and offer fine control over the chemical composition. (C) 2022 The Author(s). Published by Elsevier Ltd.