Templated Solid-State Reactions: Fundamentals to Multiple Reactions

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。有了这项技术，重要的新分子可以直接在固态下生成，而不需要有害的溶剂或昂贵的催化剂。在这项研究中，新一代的“智能材料”将用于传感器、存储设备和光学开关等应用。这项研究将整合代表性不足的群体，并不断努力招募少数族裔，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，项目负责人将主持中西部有机固体化学研讨会（MOSSCS），并将介绍一个网站，其中有本科生的实验。爱荷华大学小组与中西部三所本科学院的访问教师之间的积极合作正在进行中。项目负责人还与爱荷华市社区学区的督学、助理督学和科学协调员合作，制定一个项目，打开高中生的眼界，让他们成为科学家。该项目将包括观看广受好评的纪录片《自然痴迷》，以及项目负责人关于有机固态化学的小型ted演讲。技术概述：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体状态下组织分子反应所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，该项目将通过以下方式将模板应用于有机固体：(i)模板具有指导分子内光二聚化的一般能力，（ii）模板具有指导芳烃与烯烃的多堆光二聚化形成二聚体和低聚体的一般能力，以及（iii）模板在固体中以光二聚化和光致变色的形式支持两种反应的能力。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出现，但非常有前途和根本重要的研究途径仍未得到解决。当研究完成后，我们期望将固体中的反应更广泛地应用于有机合成（如特殊结构）、绿色化学（如无溶剂制备）、无机化学（如孔隙度）和材料科学（如多功能固体）等问题。具体来说，研究小组希望推广双核Ag(I)配合物的使用，以指导1,8-双（4-吡啶基）萘二烯的分子内光二聚化。分子内环化产生复杂的不对称[2.2]环烷和阶梯烷将被研究。在第二个目标中，吲哚咔唑将被用作引导两个以上烯烃堆叠的模板。模板将用于生成二聚体和难以获得的低聚物。在最终目标中，该团队将开发一种源自间苯二酚和水杨酸基功能的模板，该模板既指导[2+2]光二聚化，又支持分子间质子转移和异构化，从而导致光致变色。设计两种反应的方法将利用模板方法的模块化，使固体中的有机功能随时集成。

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.