CAREER: Molecular Tools to Tune the Structure-Function Properties of Nanoscale Objects by Reconfiguration of pi-Conjugated Superstructures

职业：通过重新配置 pi 共轭超结构来调整纳米级物体的结构功能特性的分子工具

• 批准号: 1941410
• 负责人: Jean Hubert Olivier
• 金额: $ 65.87万
• 依托单位: University of Miami
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-02-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1941410&HistoricalAwards=false
• 关键词: CAREER; Molecular; Tools; Tune; Structure

The research group of Jean-Hubert Olivier at The University of Miami seeks to develop new strategies to manipulate the interactions of organic molecules and polymers in nanoscale architectures (with dimensions of 1/1,000,000 meter). The overarching goal is to understand how one can precisely control assembly pathways to reconfigure the structure of organic materials and promote efficient energy transport. The results of this fundamental research have implications in solar cell design and optoelectronic devices. This project also nurtures the development of training platforms to prepare students to tackle social challenges and complex scientific problems. To achieve these goals, the Olivier group develops a Science Discovery Program: “Create and Assemble: How Nature Builds “Stuff””. The program seeks to ignite a curiosity for science and technology in younger generations, creates an environment that promotes critical thinking, motivates students across all age groups to pursue scientific careers, and sensitizes a more mature audience to the extent to which science and education can greatly contribute to a more sustainable future.With the support of the Macromolecular, Supramolecular, and Nanochemistry Program of the NSF Division of Chemistry, this project develops a new set of tools to navigate the aggregation free-energy landscape and create energetically trapped architectures equipped with structure-function properties unattainable at equilibrium. The Olivier groups seeks to establish rules and principles to manipulate the electronic structures of π-conjugated building blocks and form out-of-equilibrium states (n-doped) to tune the non-covalent interactions between superstructure precursors. From solution-phase studies that exploit spectroscopy and electrochemistry, this project seeks to understand how reconfigured superstructures promote exciton delocalization and transport. Furthermore, strategies are being developed to “lock-in” supramolecular architectures both at equilibrium, and when placed out-of-equilibrium (n-doped). Well-defined nanoscale objects created in this manner unearth a new understanding of the electronic properties enforced by electronically perturbed out-of-equilibrium states. Rules and principles are elucidated to enable, at the solid/liquid interface, the formation of hierarchical nanostructures derived from energetically trapped superstructures.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

迈阿密大学的让-休伯特·奥利维尔（Jean-Hubert Olivier）的研究小组试图开发新的策略，以操纵纳米级结构（尺寸为1/ 100万米）中有机分子和聚合物的相互作用。总体目标是了解如何精确控制组装路径以重新配置有机材料的结构并促进有效的能源运输。这项基础研究的结果对太阳能电池设计和光电子器件具有重要意义。该项目还促进了培训平台的发展，使学生能够应对社会挑战和复杂的科学问题。为了实现这些目标，奥利维尔小组开发了一个科学发现项目：“创造和组装：大自然是如何建造“东西”的”。该项目旨在点燃年轻一代对科学和技术的好奇心，创造一个促进批判性思维的环境，激励所有年龄段的学生追求科学事业，并使更成熟的观众意识到科学和教育可以在多大程度上为更可持续的未来做出贡献。在美国国家科学基金会化学部的大分子、超分子和纳米化学项目的支持下，该项目开发了一套新的工具来导航聚集的自由能景观，并创建具有平衡状态下无法实现的结构-功能特性的能量捕获结构。奥利佛小组试图建立规则和原则，以操纵π共轭构建块的电子结构，形成非平衡态（n掺杂），以调节上层结构前体之间的非共价相互作用。通过利用光谱学和电化学的溶液阶段研究，该项目旨在了解重新配置的上层结构如何促进激子的离域和输运。此外，人们正在开发策略来“锁定”处于平衡状态和处于非平衡状态（n掺杂）的超分子结构。以这种方式创建的定义良好的纳米级物体揭示了对电子摄动非平衡状态所强制的电子特性的新理解。阐明了在固体/液体界面上，由能量捕获的上层结构衍生的分层纳米结构的形成的规则和原理。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Functionalization of Electrode Surfaces with Reactive Supramolecular Oligomers Enables the Control of Monolayer Properties to Restore Electrochemical Reversibility

• DOI: 10.1021/acs.chemmater.3c01168
• 发表时间: 2023-08
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Ifigeneia Tsironi;Jarek A. Maleszka;Robert S. Wilson‐Kovacs;Victor A. Paulino;O. Acevedo;Arindam Mukhopadhyay;Jean‐Hubert Olivier

Modulating the Conduction Band Energies of Si Electrode Interfaces Functionalized with Monolayers of a Bay-Substituted Perylene Bisimide

调节用湾取代苝双酰亚胺单层功能化的硅电极界面的导带能量

• DOI: 10.1021/acs.langmuir.1c03423
• 发表时间: 2022
• 期刊: Langmuir
• 影响因子: 3.9
• 作者: Mukhopadhyay, Arindam;Liu, Kaixuan;Paulino, Victor;Olivier, Jean-Hubert
• 通讯作者: Olivier, Jean-Hubert

The Length of Molecular Tethers Can Be Used to Control the Structure and Electronic Properties of Stapled Supramolecular Polymers

• DOI: 10.1021/acs.chemmater.2c01353
• 发表时间: 2022-07
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Victor A. Paulino;Danielle M Cadena;Kaixuan Liu;Arindam Mukhopadhyay;S. Roberts;Jean‐Hubert Olivier

Leveraging the Assembly of a Rylene Dye to Tune the Semiconducting Properties of Functionalized n-Type, Hybrid Si Interfaces

利用萘嵌苯染料的组装来调节功能化 n 型混合硅界面的半导体特性

• DOI: 10.1021/acsami.0c18222
• 发表时间: 2021
• 期刊: ACS Applied Materials & Interfaces
• 影响因子: 9.5
• 作者: Mukhopadhyay, Arindam;Paulino, Victor;Liu, Kaixuan;Donley, Carrie L.;Bernard, Brianna;Shomar, Alfred;Liu, Chuan;Olivier, Jean-Hubert
• 通讯作者: Olivier, Jean-Hubert

Covalent post-assembly modification of π-conjugated supramolecular polymers delivers structurally robust light-harvesting nanoscale objects

α-共轭超分子聚合物的共价后组装修饰可提供结构坚固的光捕获纳米级物体

• DOI: 10.1039/d2nr06806k
• 发表时间: 2023
• 期刊: Nanoscale
• 影响因子: 6.7
• 作者: Paulino, Victor;Liu, Kaixuan;Cesiliano, Valentino;Tsironi, Ifigeneia;Mukhopadhyay, Arindam;Kaufman, Maria;Olivier, Jean-Hubert
• 通讯作者: Olivier, Jean-Hubert