Templated Solid-State Reactions: Fundamentals to Multiple Reactions

模板化固态反应：多重反应的基础

• 批准号: 1408834
• 负责人: Leonard MacGillivray
• 金额: $ 42.6万
• 依托单位: University of Iowa
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-07-01 至 2017-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1408834&HistoricalAwards=false
• 关键词: Templated; Solid; State; Reactions; Fundamentals

Non-Technical Summary The research activities focus on using small molecules to serve as templates to carefully position organic molecules in crystalline solids allowing for better control and improved properties of solid-state materials that undergo chemical reactions. With this technique, important new molecules can be generated directly in the solid state without the need for harmful solvents or expensive catalysts. New generations of "smart materials" will be prepared in this study for use in applications such as sensors, memory devices, and optical switches. The research will integrate underrepresented groups with ongoing efforts to recruit minorities, and the group will continue to develop three undergraduate laboratory experiments at the University of Iowa. As part of these activities, the project leader will host the Midwest Organic Solid State Chemistry Symposium (MOSSCS) and will introduce a website that has the undergraduate experiments. Active collaborations between the Iowa group and visiting faculty at three undergraduate colleges in the Midwest are ongoing. The project lead is also working with the Superintendent, Assistant Superintendent, and Science Coordinator of the Iowa City Community School District to develop a program that opens the eyes of high-school students to careers as scientists. The program will involve viewings of the critically acclaimed documentary Naturally Obsessed and a mini-TED talk by the project leader on organic solid-state chemistry.Technical Summary:The general goal of this project is to apply small-molecule and dinuclear metal-organic templates to address fundamental problems and challenges that confront chemists to organize molecules to react in the organic solid state. With support from the Solid State and Materials Chemistry program in the Division of Materials Research, the project will apply templates to organic solids by determining: (i) a general ability of templates to direct intramolecular photodimerizations, (ii) a general ability of templates to direct multiple stacks of aromatics with olefins that photodimerize to give both dimers and oligomers, and (iii) the ability of a template to support two reactions in a solid in the form of a photodimerization and photochromism. The research is motivated by the fact that although templates are rapidly emerging as tools to control reactivity in solids, highly-promising and fundamentally important avenues of needed investigation remain unaddressed. When the research is completed, we expect that it will be possible to more broadly apply reactions in solids to problems of organic synthesis (e.g. unusual architectures), green chemistry (e.g. solvent-free preparation), inorganic chemistry (e.g. porosity), and materials science (e.g. multifunctional solids). Specifically, the research team expects to generalize the use of dinuclear Ag(I) complexes to direct intramolecular photodimerizations of a 1,8-bis(4-pyridyl)naphthyl diene. Intramolecular cyclizations that afford complex unsymmetrical [2.2]cyclophanes and ladderanes will be studied. In a second aim, indolocarbazoles will be employed as templates that direct stacks of more than two olefins. Templates will be used to generate both dimers and difficult-to-achieve oligomers. In a final aim, the team will develop a template derived from resorcinol and salicylidene functionalities that both directs a [2+2] photodimerization and supports an intermolecular proton transfer and isomerization that leads to photochromism. The approach to engineer two reactions will take advantage of the modularity of the template method that enables ready integration of organic functionality in solids.

非技术摘要 研究活动的重点是使用小分子作为模板，将有机分子仔细定位在结晶固体中，从而更好地控制和改善经历化学反应的固态材料的性能。 通过这项技术，可以直接以固态生成重要的新分子，而不需要有害的溶剂或昂贵的催化剂。这项研究将准备新一代“智能材料”，用于传感器、存储设备和光开关等应用。 该研究将把代表性不足的群体与招募少数族裔的持续努力结合起来，该小组将继续在爱荷华大学开展三个本科生实验室实验。 作为这些活动的一部分，项目负责人将主办中西部有机固态化学研讨会（MOSSCS），并将介绍一个包含本科生实验的网站。 爱荷华州小组与中西部三所本科院校的访问教师之间的积极合作正在进行中。 该项目负责人还与爱荷华市社区学区的院长、助理院长和科学协调员合作，制定一项计划，让高中生开启科学家职业生涯。 该计划将包括观看广受好评的纪录片《Naturally Obsessed》以及项目负责人关于有机固态化学的迷你 TED 演讲。 技术摘要：该项目的总体目标是应用小分子和双核金属有机模板来解决化学家在有机固态中组织分子进行反应时面临的基本问题和挑战。 在材料研究部固态和材料化学项目的支持下，该项目将通过确定以下内容将模板应用于有机固体：（i）模板引导分子内光二聚化的一般能力，（ii）模板引导多个芳香族化合物与烯烃光二聚化产生二聚体和低聚物的一般能力，以及（iii）模板支持一个反应中的两个反应的能力。 以光二聚和光致变色形式存在的固体。 这项研究的动机是，尽管模板作为控制固体反应性的工具正在迅速兴起，但所需研究的高前景和根本上重要的途径仍未得到解决。 研究完成后，我们预计固体反应将有可能更广泛地应用于有机合成（例如不寻常的结构）、绿色化学（例如无溶剂制备）、无机化学（例如孔隙率）和材料科学（例如多功能固体）等问题。 具体来说，研究小组希望推广使用双核Ag(I)配合物来指导1,8-双(4-吡啶基)萘二烯的分子内光二聚化。 将研究提供复杂的不对称[2.2]环烷和梯烷的分子内环化。 第二个目标是，吲哚并咔唑将用作模板，直接堆叠两种以上的烯烃。 模板将用于生成二聚体和难以实现的寡聚体。 最终目标是，该团队将开发一种源自间苯二酚和水杨基官能团的模板，该模板既能指导 [2+2] 光二聚化，又能支持导致光致变色的分子间质子转移和异构化。 设计两个反应的方法将利用模板方法的模块化优势，从而能够轻松集成固体中的有机功能。