ULISSE - Using Electrostatic Interactions to Control Supramolecular Self-Assembly at Surfaces

ULISSE - 利用静电相互作用控制表面超分子自组装

• 批准号: EP/G044864/1
• 负责人: Alessandro De Vita
• 金额: $ 45.45万
• 依托单位: King's College London
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2010
• 资助国家: 英国
• 起止时间: 2010 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FG044864%2F1
• 关键词: ULISSE; Using; Electrostatic; Interactions; Control

A major promise made by Nanotechnology Research to contemporary society is that next-generation molecular-scale devices will be faster, more versatile and more energy efficient than the ones based on current technology. Organic molecules are among the best candidate bricks for future nanoscale device fabrication. Their chemical structure can be easily modified, suggesting that carefully designed molecules could in principle assemble spontaneously into any desired structure, with no need of top down intervention. The optimisation by design of the chemical linkage between molecules has been, correspondently, an extensively explored concept in the molecular self-assembly field, albeit in some way limited in its scope by the short-range character of the bonding. Very recent research suggests that controlling the state of charge of organic molecules may provide a further direct handle to determine the assembly features on larger scales, through the contribution of long-range electrostatic interactions. However, this possibility is still virtually unexplored, in spite of its potential impact on nanofabrication. The electronic properties of molecular organic materials are, meanwhile, also attracting a massive, and ever growing, interest. Indeed, Organic Electronics is currently a booming field, with novel light-emission and light-energy conversion applications of strategic importance for society being investigated and early devices being produced. Once more, some crucial properties of these devices are determined by processes occurring at the nanometre scale and involve electrostatic interactions. Charge transfer between a metal surface and a layer of organic molecules deposited on it is known, e.g., to control the electric conduction properties of a metal-organic contact. However, no consensus has been reached yet on how to model such metal-organic interfaces properly, and device design is often a trial-and-error process.The present project will study charge transfer processes between organic molecules and metallic substrates, and their connection with self-assembly. Using both theory and experiment, we will investigate if these processes can be predicted and controlled by appropriate choices of molecules, substrates and coverages. The work will be useful for both understanding fundamental principles of molecular self-organisation and for unravelling the fundamental mechanisms that govern energy level alignment at metal-organic interfaces. Crucially, the whole will be much more than the sum of the parts. Namely, starting from charge transfer and pursuing the self-assembly route, we will determine if long-range forces between charged molecules can drive the spontaneous formation of novel classes of supramolecular structures. This would represent a novel tool for predicting and controlling the assembly. Conversely, starting from the observed assembly and pursuing the Organic Electronic route, we will investigate if specific molecular linkage patterns can reveal the occurrence of charge transfer. This would provide a novel route to precious information on the electronic properties of metal-organic interfaces. Electronic structure calculations, photoemission spectroscopy experiments, molecular dynamics simulations, and scanning tunnelling microscopy imaging will be used throughout the investigation. This will link two strategic fields of research which can greatly benefit from each other, namely nanofabrication by supramolecular assembly and molecular electronics, for the first time in an integrated UK-based project.

纳米技术研究对当代社会的一个主要承诺是，下一代分子级设备将比基于现有技术的设备更快、更多功能、更节能。有机分子是未来制造纳米器件的最佳候选材料之一。它们的化学结构可以很容易地修改，这表明精心设计的分子原则上可以自发组装成任何所需的结构，不需要自上而下的干预。相应地，通过设计分子间化学键的优化已经成为分子自组装领域中一个被广泛探索的概念，尽管其范围在某种程度上受到成键的短程特性的限制。最近的研究表明，通过远程静电相互作用的贡献，控制有机分子的电荷状态可能会为在更大范围内确定组装特征提供进一步的直接手段。然而，这种可能性实际上仍然没有被探索，尽管它对纳米制造有潜在的影响。与此同时，分子有机材料的电子性质也吸引了人们巨大的兴趣，而且还在不断增长。事实上，有机电子学目前是一个蓬勃发展的领域，人们正在研究对社会具有战略意义的新型光发射和光能转换应用，并正在生产早期设备。再一次，这些设备的一些关键属性是由纳米级的过程决定的，涉及静电相互作用。金属表面和沉积在其上的有机分子层之间的电荷转移是已知的，例如，控制金属-有机接触的导电性质。然而，对于如何正确地模拟这种金属-有机界面，目前还没有达成共识，而且器件设计往往是一个反复尝试的过程。本项目将研究有机分子和金属衬底之间的电荷转移过程，以及它们与自组装的关系。通过理论和实验，我们将研究是否可以通过适当选择分子、底物和覆盖物来预测和控制这些过程。这项工作将有助于理解分子自组织的基本原理，并有助于揭示支配金属-有机界面能级排列的基本机制。至关重要的是，整体将远远超过各部分的总和。也就是说，从电荷转移出发，追寻自组装路线，我们将确定带电分子之间的长程力是否能够驱动新型超分子结构的自发形成。这将代表一种预测和控制组件的新工具。相反，我们将从观察到的组装出发，沿着有机电子路线，研究特定的分子连接模式是否能够揭示电荷转移的发生。这将为获得有关金属-有机界面电子性质的宝贵信息提供一条新的途径。电子结构计算、光电子能谱实验、分子动力学模拟和扫描隧道显微镜成像将在整个研究过程中使用。这将把两个可以相互受益的战略研究领域联系起来，即超分子组装纳米制造和分子电子学，这将是英国第一次在一个综合项目中这样做。

项目成果

Self-assembly of decoupled borazines on metal surfaces: the role of the peripheral groups.

• DOI: 10.1002/chem.201402839
• 发表时间: 2014-09-08
• 期刊: Chemistry (Weinheim an der Bergstrasse, Germany)
• 作者: Kalashnyk N;Ganesh Nagaswaran P;Kervyn S;Riello M;Moreton B;Jones TS;De Vita A;Bonifazi D;Costantini G
• 通讯作者: Costantini G

A long-range ordered array of copper tetrameric units embedded in an on-surface metal organic framework.

嵌入表面金属有机框架中的铜四聚体单元的长程有序阵列。

• DOI: 10.1063/1.5004082
• 发表时间: 2017
• 期刊: The Journal of chemical physics
• 作者: Lo Cicero M

Anomalous coarsening driven by reversible charge transfer at metal-organic interfaces.

• DOI: 10.1021/nn505063w
• 发表时间: 2014-12-23
• 期刊: ACS NANO
• 影响因子: 17.1
• 作者: Della Pia, Ada;Riello, Massimo;Floris, Andrea;Stassen, Daphne;Jones, Tim S.;Bonifazi, Davide;De Vita, Alessandro;Costantini, Giovanni
• 通讯作者: Costantini, Giovanni

Two-Dimensional Ketone-Driven Metal-Organic Coordination on Cu(111).

• DOI: 10.1002/chem.201600368
• 发表时间: 2016-06-06
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Della Pia, Ada;Riello, Massimo;Lawrence, James;Stassen, Daphne;Jones, Tim S.;Bonifazi, Davide;De Vita, Alessandro;Costantini, Giovanni
• 通讯作者: Costantini, Giovanni