CAREER: Framework Topology Dependent Photophysical Properties of Chromophore Assemblies within Metal-Organic Frameworks

在这个由化学系化学结构、动力学和机理b项目资助的CAREER项目中，南伊利诺伊大学卡本代尔分校化学和生物化学系的Pravas Deria教授正在开发高度着色的有机分子的组装，这些有机分子被精心排列成特定的结构（称为金属-有机框架）。这些金属有机框架和光反应时具有独特的性质。这项研究的目标是使框架组合物具有捕获和特定通道光的能力，从而有效地收集光并将其转化为存储的化学能。通过这项职业研究获得的知识将通过增强年轻学生（高中及以下）对基础科学的认知，对伊利诺伊州南部产生广泛的影响。Deria教授将招募当地高中学生参加为期两周的化学研究营，在那里他们将接触基础科学研究，包括使用令人兴奋的现代仪器的实践经验。中学生们将在当地的一个科学中心参与用生物分子色素进行的“颜色科学”演示。这些教育项目将提供第一手的经验，激励学生选择科学事业。该项目处于无机化学、有机化学和物理化学的交叉点，非常适合各级科学家的教育，因为该项目适用于太阳能、燃料、清洁能源技术。由于要求超分子合成设计，在人工化学组件中实现高效光子能量收集的光系统ii类光物理行为是一项挑战。精确和可控的颜料组织是实现与简单的发色团聚集体功能不同的新组合物的先决条件。多孔晶体金属有机框架（mof）提供了独特的平台来开发定义良好，溶液稳定的分子发色团组件，具有高效的光子能量转导功能。然而，在明确定义的mof中设计和控制理想的光系统ii类光物理行为尚处于发现的早期阶段。激子形成的基本规则，远程激子传播，并指导激子分裂成工作产生电荷在这些合成框架组件需要完全建立。这个CAREER项目探索了新的MOF组合物，它可以作为框架拓扑的函数来控制激子结构和动力学，并阐明了发色团电子结构和激发态对称性如何影响激子的离域和迁移。该研究可能揭示影响单重态-三重态系统间交叉量子产率的关键因素。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。

In this CAREER project, funded by the Chemical Structure, Dynamics, & Mechanisms-B Program of the Chemistry Division, Professor Pravas Deria of the Department of Chemistry & Biochemistry at Southern Illinois University Carbondale is developing assemblies of highly colored organic molecules carefully arranged in specific structures (known as metal-organic frameworks). These Metal-organic frameworks have unique properties when they react with light. The goal of this research is to make framework compositions with the ability to capture and specifically channel light for efficient light harvesting and conversion into stored chemical energy. The knowledge gained through this CAREER research will have a broad impact in southern Illinois by augmenting young student's (high school and below) perception towards basic science. Professor Deria will recruit regional high school (HS) students into a two-week chemistry research camp, where they will be introduced to fundamental scientific research --including hands-on experience with exciting modern instrumentation. Middle school students will be involved in demonstration of the 'Science of Colors' with molecular pigments in biology at a local Science Center. These educational programs will provide firsthand experience to inspire students to choose science careers. The project lies at the interface of inorganic, organic, and physical chemistry, and is well suited for the education of scientists at all levels as the project has applications to solar to fuels, clean energy technologies. Achieving photosystem II-like photophysical behavior for efficient photonic energy harvesting in artificial chemical assemblies is a challenge due to demanding supramolecular synthetic designs. Precise and controllable organization of pigments is a prerequisite to achieving new compositions that function differently than simple chromophore aggregates. Porous crystalline metal-organic frameworks (MOFs) offer unique platforms to develop well-defined, solution-stable molecular chromophore assemblies with efficient photon energy transducing functionality. However, the design and control of desirable photosystem II-like photophysical behavior in well-defined MOFs is at an early stage of discovery. Basic rules governing exciton formation, long-range exciton propagation, and directing exciton splitting into work-producing charges within these synthetic framework-assemblies need to be fully established. This CAREER project explores novel MOF compositions that control excitonic structure and dynamics as a function of framework topology and elucidates how chromophore electronic structure and excited-state symmetry impacts exciton delocalization and migration. The research may unveil the critical factors that modulate singlet-triplet intersystem crossing quantum yields.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.