A-Nor: New Concepts for the Norbornadiene/Quadricyclane (NBD/QC) Interconversion

A-Nor：降冰片二烯/四环烷 (NBD/QC) 相互转化的新概念

• 批准号: 517990659
• 负责人: Professor Dr. Andreas Hirsch
• 金额: --
• 依托单位: Lehrstuhl für Organische Chemie II
• 依托单位国家: 德国
• 项目类别: Research Units
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/517990659?language=en
• 关键词: Nor; New; Concepts; Norbornadiene; Quadricyclane

For the design and optimization of future MOST systems, precise chemical fine-tuning as well as comprehensive understanding of the photochemical isomerization mechanism is of major importance. Therefore, the syntheses of new norbornadiene/quadricyclane (NBD/QC) derivatives and the development of efficient and unprecedented catalytically triggered energy release processes is targeted. Based on the NBD/QC interconversion couple, as well as chromophore-mostophore hybrid structures, our goal is to optimize the molecular architectures and system properties in order to approach competitive MOST applications while simultaneously generating new insights into the fundamental mechanistics of the underlying photoisomerization and energy release processes. For this purpose, our proposal will consist of three work-packages. The thrust of work-package 1 is to generate a library of new NBD/QC couples and their related heterocyclic analogues containing e.g. oxygen or nitrogen in the bridge. Consequently, the focus is to perform tailored functionalization of NBD/QC couples to obtain optimized photophysical properties, which are necessary for future applications. The synthesis of novel rylene-norbornadiene hybride structures as model compounds for fully photo-switchable systems is the task of work package 2. This will help to unravel the fundamental switching process and generate comprehensive understanding of the underlying photophysical mechanism, thus allowing for precise chemical tuning of the related properties of NBD/QC couples. In work-package 3, both the [2+2] photocyclization from NBD to QC and the catalytic back-conversion within shell-by-shell functionalized nanoparticles and their confined space in the bilayer, will be investigated. Therefore, tailor-made functionalized nanoparticles will be used as a) quasi-homogeneous catalysts, b) platforms providing a tunable confined space reaction scenario and c) as phase-transfer mediators allowing for example to operate in aqueous solutions. Through the conscientious processing of the proposed work-packages, three main research questions will be investigated: (i) How can we design and optimize NBD/QC couples as suitable MOST systems with low synthetic effort and efficient reaction procedures? (ii) How do we implement the fundamental mechanistic understanding to unravel the key factors limiting the relevant MOST properties such as energy storage density? (iii) How can we maximize the efficiency of the catalytic energy release trigged by tailor-made nanoparticle-based catalysts and what are the main challenges by using such systems for practical applications? As essential part within FOR MOST, our project will push forward the future MOST technology by providing a series of novel norbornadiene-based energy storage systems, model compounds for the investigation of fundamental mechanistics and nanoparticle-based catalysts to trigger the energy release reaction.

对于未来MOST系统的设计和优化，精确的化学微调以及对光化学异构化机理的全面理解是非常重要的。因此，合成新的降冰片二烯/四环烷（NBD/QC）衍生物和开发高效和前所未有的催化触发能量释放过程的目标。基于NBD/QC相互转换对，以及发色团-mostophore杂化结构，我们的目标是优化分子结构和系统性质，以接近有竞争力的MOST应用，同时产生新的见解的基础光异构化和能量释放过程的基本机理。为此，我们的建议将包括三个工作包。工作包1的主旨是产生新的NBD/QC对及其相关的杂环类似物的文库，例如在桥中含有氧或氮。因此，重点是进行定制的官能化的NBD/QC夫妇，以获得优化的物理性能，这是必要的，为未来的应用。作为完全光开关系统的模型化合物的新型萘嵌苯-降冰片二烯杂化结构的合成是工作包2的任务。这将有助于解开基本的开关过程，并产生对潜在的电子物理机制的全面理解，从而允许精确的化学调谐NBD/QC对的相关性质。在工作包3中，将研究从NBD到QC的[2+2]光环化和逐壳功能化纳米颗粒内的催化反向转化及其在双层中的受限空间。因此，定制的官能化纳米颗粒将用作a）准均相催化剂，B）提供可调受限空间反应方案的平台和c）作为允许例如在水溶液中操作的相转移介质。通过认真处理拟议的工作包，三个主要的研究问题将被调查：（一）我们如何设计和优化NBD/QC夫妇合适的MOST系统与低合成工作量和有效的反应程序？(ii)我们如何实现基本的机械理解，以解开限制相关MOST属性（如储能密度）的关键因素？(iii)我们如何才能最大限度地提高量身定制的基于纳米颗粒的催化剂所释放的催化能量的效率，以及将此类系统用于实际应用的主要挑战是什么？作为FOR MOST的重要组成部分，我们的项目将通过提供一系列新颖的基于降冰片二烯的储能系统，用于基础机理研究的模型化合物和基于纳米颗粒的催化剂来触发能量释放反应，从而推动未来的MOST技术。