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Supramolecular Approaches to Control Reactivity in the Organic Solid State

控制有机固态反应性的超分子方法

基本信息

批准号：
1708673
负责人：
Leonard MacGillivray
金额：
$ 40万
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：
2017
资助国家：
美国
起止时间：
2017-07-01 至 2023-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1708673&HistoricalAwards=false
关键词：
Supramolecular Approaches Control Reactivity Organic

项目摘要

Nontechnical Abstract:The general goal of this project is to increase the value of chemical reactions conducted in the organic solid state. Synthetic chemistry is an underpinning in chemical science that enables advancements in society as related to developing new medicines (e.g. active pharmaceutics) and technologically-important materials (e.g. strong and lightweight). This project will develop strategies to synthesize molecules in which chemical reactions are conducted in the solid state. Whereas synthetic chemistry is typically performed in the liquid phase or solution, the solvent-free and "frozen" environment of the solid state provides opportunities to synthesize molecules with unique structures and properties. Strategies to conduct reactions in organic solids can, thereby, accelerate progress of how synthetic chemistry defines and is applied to developments in society and technology. The project will integrate underrepresented groups, develop undergraduate laboratory experiments, and maintain active collaborations with undergraduate colleges. The project will also introduce middle-school students to careers in chemical science (e.g. X-ray crystallography).Technical Abstract:This project will increase the value of reactions conducted in solids by developing solid-state reactions that generate products with synthetically-valuable organic functional groups and/or are based on reduced symmetries. The research will apply multi-component solids in the form of cocrystals and/or metal-organic materials to direct the solid-state reactions. Specifically, (i) metal-organic solids will direct photodimerizations of imines that form cyclobutanes lined exclusively with aldehyde groups, (ii) cocrystals will direct photodimerizations that generate unsymmetrical ladderanes, and (iii) cocrystals will support cross-photocycloadditions. The research is motivated by the fact that although multi-component solids are rapidly emerging as media to reliably control reactivity in solids relative to the liquid phase, important avenues of needed investigation based on forming products decorated with challenging organic functional groups and of reduced symmetry remain unaddressed. When the proposed research is completed, it will be possible to more broadly apply reactions in solids to problems of organic synthesis (e.g. complex molecules), green chemistry (e.g. solvent-free preparation), inorganic chemistry (e.g. metal-organic reactivity), and materials science (e.g. single-crystal reactions).

非技术摘要：本项目的总体目标是提高在有机固态中进行的化学反应的价值。合成化学是化学科学的基础，能够促进与开发新药（例如活性药物）和技术重要材料（例如坚固和轻质）相关的社会进步。该项目将开发合成分子的策略，其中化学反应在固态下进行。虽然合成化学通常在液相或溶液中进行，但固态的无溶剂和“冷冻”环境提供了合成具有独特结构和性质的分子的机会。因此，在有机固体中进行反应的策略可以加速合成化学如何定义和应用于社会和技术发展的进步。该项目将整合代表性不足的群体，开发本科实验室实验，并保持与本科院校的积极合作。该项目还将向中学生介绍化学科学的职业（例如X射线晶体学）。技术摘要：该项目将通过开发固态反应来增加在固体中进行的反应的价值，该反应生成具有合成价值的有机官能团和/或基于减少的对称性的产物。该研究将以共晶和/或金属有机材料的形式应用多组分固体来指导固态反应。具体地，（i）金属有机固体将引导亚胺的光二聚，其形成仅与醛基团对齐的环丁烷，（ii）共晶将引导产生不对称梯形烷的光二聚，和（iii）共晶将支持交叉光环加成。该研究的动机是这样一个事实，即虽然多组分固体正在迅速出现作为介质，以可靠地控制反应性的固体相对于液相，所需的调查的基础上形成具有挑战性的有机官能团和降低对称性的装饰产品的重要途径仍然没有得到解决。当拟议的研究完成后，将有可能更广泛地将固体中的反应应用于有机合成（例如复杂分子）、绿色化学（例如无溶剂制备）、无机化学（例如金属-有机反应性）和材料科学（例如单晶反应）的问题。

项目成果

期刊论文数量（40）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

DFT Computed Dielectric Response and THz Spectra of Organic Co-Crystals and Their Constituent Components

DFT 计算有机共晶及其组成成分的介电响应和太赫兹光谱

DOI：
10.3390/molecules24050959
发表时间：
2019
期刊：
Molecules
影响因子：
4.6
作者：
Bennett, Joseph;Raglione, Michaella;Oburn, Shalisa;MacGillivray, Leonard;Arnold, Mark;Mason, Sara
通讯作者：
Mason, Sara

Semiconductor Cocrystals Based on Boron: Generated Electrical Response with π-Rich Aromatic Molecules

DOI：
10.1021/acs.cgd.9b00953
发表时间：
2020-01-01
期刊：
CRYSTAL GROWTH & DESIGN
影响因子：
3.8
作者：
Ray, Kamal K.;Campillo-Alvarado, Gonzalo;Tivanski, Alexei V.
通讯作者：
Tivanski, Alexei V.

Application of a tetrapyrimidyl cyclobutane synthesized in the organic solid state: a halogen-bonded supramolecular ladder

有机固态合成四嘧啶基环丁烷的应用：卤素键合超分子梯

DOI：
10.1039/d0ce01280g
发表时间：
2020
期刊：
CrystEngComm
影响因子：
3.1
作者：
Sinnwell, Michael A.;Santana, Carlos L.;Bosch, Eric;MacGillivray, Leonard R.;Groeneman, Ryan H.
通讯作者：
Groeneman, Ryan H.

Diversifying molecular and topological space via a supramolecular solid-state synthesis: a purely organic mok net sustained by hydrogen bonds

DOI：
10.1107/s2052252519011382
发表时间：
2019-11-01
期刊：
IUCRJ
影响因子：
3.9
作者：
Oburn, Shalisa M.;Sinnwell, Michael A.;MacGillivray, Leonard
通讯作者：
MacGillivray, Leonard

Superstructural diversity in salt-cocrystals: higher-order hydrogen-bonded assemblies formed using U-shaped dications and with assistance of π − –π stacking

盐共晶的上层结构多样性：使用 U 形双键并在 α β β 堆叠的帮助下形成的高阶氢键组装体

DOI：
10.1039/d0cc02671a
发表时间：
2020
期刊：
Chemical Communications
影响因子：
4.9
作者：
Yelgaonkar, Shweta P.;Kiani, Daniyal;Baltrusaitis, Jonas;MacGillivray, Leonard R.
通讯作者：
MacGillivray, Leonard R.