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.

研究活动的重点是使用小分子作为模板，在结晶固体中仔细定位有机分子，从而更好地控制和改善发生化学反应的固态材料的性能。 通过这种技术，可以直接在固态下产生重要的新分子，而不需要有害的溶剂或昂贵的催化剂。新一代的“智能材料”将在这项研究中准备用于传感器，存储设备和光开关等应用。 这项研究将把代表性不足的群体与正在进行的招募少数族裔的努力结合起来，该小组将继续在爱荷华州大学开展三项本科生实验室实验。 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），并将介绍一个网站，有本科生的实验。 爱荷华州小组与中西部三所本科院校的客座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州市社区学区的负责人、助理负责人和科学协调员合作，制定一项计划，让高中生对科学家的职业生涯有一个新的认识。 该项目将包括观看广受好评的纪录片《Naturally Obsessed》，以及由项目负责人在有机固态化学方面的小型TED演讲。技术概要：本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反应所面临的基本问题和挑战。 在材料研究部门的固态和材料化学计划的支持下，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的一般能力，（ii）模板引导芳族化合物与烯烃的多个叠层的一般能力，所述芳族化合物与烯烃光二聚以产生二聚物和低聚物，和（iii）模板在固体中支持光二聚和光致变色形式的两个反应的能力。 这项研究的动机是这样一个事实，即虽然模板正在迅速成为控制固体反应性的工具，但所需调查的非常有前途和根本重要的途径仍然没有得到解决。 当研究完成后，我们预计将有可能更广泛地将固体中的反应应用于有机合成（例如不寻常的结构），绿色化学（例如无溶剂制备），无机化学（例如多孔性）和材料科学（例如多功能固体）的问题。 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反应。 将研究提供复杂的不对称[2.2]环番和梯形的分子内环化。 在第二个目标中，吲哚并咔唑将被用作引导多于两种烯烃的堆叠的模板。 模板将用于生成二聚体和难以实现的寡聚体。 在最终目标中，该团队将开发一种源自间苯二酚和亚水杨基官能团的模板，该模板既可以指导[2+2]光二聚化，又可以支持分子间质子转移和异构化，从而导致光致变色。 设计两个反应的方法将利用模板方法的模块性，该模块性使得能够在固体中容易地整合有机官能团。