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.

非技术总结研究活动着重于使用小分子作为模板，以仔细地将有机分子定位在晶体固体中，从而可以更好地控制和改善经历化学反应的固态材料。 通过这种技术，重要的新分子可以直接以固态生成，而无需有害溶剂或昂贵的催化剂。新一代的“智能材料”将在本研究中准备，以用于传感器，内存设备和光学开关等应用。 这项研究将使代表性不足的团体与持续招募少数民族的努力相结合，该小组将继续在爱荷华大学开发三个本科实验室实验。 作为这些活动的一部分，项目负责人将举办中西部有机固态化学研讨会（MOSSC），并将介绍一个具有本科实验的网站。 爱荷华州小组与中西部三所本科学院的教职员工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校长，助理院长和科学协调员合作，开发了一项计划，该计划将高中生的目光敞开了看法。 该计划将涉及对有机固态化学的项目负责人自然痴迷的备受赞誉的纪录片的观看。技术摘要：该项目的一般目标是应用小分子和二核金属金属有机模板，以解决固定化学剂的基本化学疗法，以解决固定分子的基础化，以解决固定的分子。 在材料研究划分中的固态和材料化学计划的支持下，该项目将通过确定模板将模板应用于有机固体中：（i）模板直接直接分子内光二聚体化的一般能力，（ii）模板可以将模板与两种芳香族的多个反应能力和奥利格的能力相关的芳香剂的多个芳香剂直接的一般能力（iii inii inii inii inii inii inii inii ii iimers andii inii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii s，（固体以光二聚化和光致变色的形式。 这项研究是由于模板迅速成为控制固体中反应性的工具，但所需研究的高度和根本重要的途径仍未得到满足。 研究完成后，我们希望有可能在固体中更广泛地将反应应用于有机合成问题（例如，不寻常的架构），绿色化学（例如无溶剂化学制剂），无机化学（例如孔隙率）和材料科学（例如，多功能固体）。 具体而言，研究小组希望概括使用双核AG（I）复合物来指导1,8-双（4-吡啶基）萘二烯的分子内光二聚会。 将研究具有复杂不对称的[2.2]环媒体和梯形的分子内环化。 在第二个目的中，吲哚前唑将被用作直接堆叠两个以上烯烃的模板。 模板将用于生成二聚体和难以实现的低聚物。 在最终目的中，团队将开发一个源自分辨酚和水杨烯功能的模板，该模板既指导[2+2]光二聚化并支持分子间质子转移和异构化，从而导致光色素。 对工程师进行两种反应的方法将利用模板方法的模块化，从而可以准备地整合固体中的有机功能。