CAREER: Studies of Chalcogen Bonding-Mediated Assembly towards Porous Crystalline Frameworks, Hierarchical Assemblies, and Multicomponent Materials

职业：硫族键介导的多孔晶体框架组装、分级组装和多组分材料的研究

• 批准号: 2143623
• 负责人: Christopher McGuirk
• 金额: $ 76.04万
• 依托单位: Colorado School of Mines
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-02-01 至 2027-01-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2143623&HistoricalAwards=false
• 关键词: CAREER; Studies; Chalcogen; Bonding; Mediated

This award is funded in whole or in part under the American Rescue Plan Act of 2021 (Public Law 117-2).Non-Technical Abstract: Discoveries of new materials have led to seismic advances in our societies. These advances typically occur through breakthroughs with one of two key components of materials: the repeating individual molecular or atomic building block or the way individual components are connected. Such materials can be considered analogous to a brick wall, with the bricks as the repeating blocks, and the mortar connecting them together. While an enormous diversity of building blocks is known, only a handful of established modes of connectivity exist. Generally, each different mode of connectivity allows the creation of an entire new class of materials. Perhaps the best example for this is the field of nanoporous frameworks, which are sponge-like materials containing voids slightly larger than individual molecules. Nanoporous frameworks containing similar bricks, but connected through different mortars, show vastly different behaviors, each type exhibiting a unique combination of properties. With support from the Solid State and Materials Chemistry program in the Division of Materials Research, the principal investigator and their research group develop a new class of nanoporous frameworks enabled by a recently discovered mode of connectivity. In doing so, the principal investigator advances our knowledge of connectivity in materials, particularly by advancing the understanding of this nascent connectivity, realizing unparalleled structural complexities in materials, and developing a class of materials with a hitherto unseen set of properties. To help teach the core concepts of how building blocks assemble into materials, the investigators also develop and disseminate an inexpensive and highly modular model kit exercise. This level-adaptable game uses multi-colored modeling clay and toothpicks to teach students how the bricks and mortar work together to form materials. To reduce inequalities in upper-division chemistry offerings between research universities and URM-serving primarily undergraduate institutions (PUIs), the principal investigator develops and offers a hybrid upper-division Physical Organic course that is simultaneously taught face-to-face at Colorado School of Mines and remotely to students at institutions across Colorado. Technical Abstract: The manner of bonding between constituent atoms or molecules invariably influences the properties of materials. Perhaps no material family is more emblematic of this than synthetic porous frameworks, wherein the properties, and thus utility, of a given subclass rely heavily on the directionality, dynamic reversibility, and net strength of the intermolecular interactions used. Therefore, the discovery and characterization of alternative modes of intermolecular assembly that may give rise to complementary material classes are of great interest. The primary objective of this project is to explore if chalcogen bonding, a recently defined non-covalent interaction, can deliberately and reliably assemble molecular tectons into low-density crystalline framework materials, towards the realization of a new class of frameworks: Chalcogen-Bonded Organic Frameworks, i.e. ChOFs. Empirical and computational studies of chalcogen bond-mediated assembly in model systems establish a set of quantitative guidelines for the rational design of permanently porous ChOFs with topologies predictively assembled from the molecular tecton structure and crystallization conditions. These insights lead to compositionally hierarchical and ordered multi-component materials, elusive features in established framework classes. Solution-phase association studies, such as NMR spectroscopy and ITC, and DFT-based calculations are used to quantify chalcogen bonding between synthesized tectons; the atomic structure of assembled frameworks is characterized by single-crystal XRD. An inexpensive and highly modular model kit exercise using modeling clay and toothpicks is developed and disseminated to students with the intent to teach core concepts of molecular assembly and crystal engineering. To reduce inequalities in upper-division chemistry offerings between research universities and URM-serving PUIs, the principal investigator develops and offers a hybrid upper-division Physical Organic course that is simultaneously taught face-to-face at Colorado School of Mines and remotely to students at institutions across Colorado.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

该奖项全部或部分由2021年美国救援计划法案（公法117-2）资助。非技术摘要：新材料的发现导致了我们社会的巨大进步。这些进展通常是通过材料的两个关键组成部分之一的突破而实现的：重复的单个分子或原子构建块或单个组成部分的连接方式。这种材料可以被认为类似于砖墙，砖块作为重复块，砂浆将它们连接在一起。虽然已知的构件种类繁多，但只有少数几种既定的连接模式。通常，每种不同的连接模式都允许创建一个全新的材质类别。也许这方面最好的例子是纳米多孔框架领域，纳米多孔框架是海绵状材料，含有比单个分子稍大的空隙。含有类似砖块的纳米多孔框架，但通过不同的砂浆连接，表现出截然不同的行为，每种类型都表现出独特的性能组合。在材料研究部门的固态和材料化学计划的支持下，主要研究员和他们的研究小组开发了一类新的纳米多孔框架，该框架由最近发现的连接模式实现。在这样做的过程中，首席研究员推进了我们对材料中连接性的认识，特别是通过推进对这种新生连接性的理解，实现材料中无与伦比的结构复杂性，并开发出一类具有迄今为止未见的一系列特性的材料。为了帮助教授积木如何组装成材料的核心概念，研究人员还开发和传播了一种廉价且高度模块化的模型套件练习。这个水平适应游戏使用多色建模粘土和牙签教学生如何砖和砂浆一起工作，形成材料。为了减少研究型大学和URM服务的主要本科院校（PUI）之间的上师化学课程的不平等，主要研究者开发并提供了一个混合的上师物理有机课程，该课程同时在科罗拉多矿业学院面对面授课，并远程向科罗拉多各机构的学生授课。技术摘要：组成原子或分子之间的键合方式总是影响材料的性能。也许没有材料家族比合成多孔框架更能代表这一点，其中给定亚类的性质和效用严重依赖于所使用的分子间相互作用的方向性、动态可逆性和净强度。因此，分子间组装的替代模式的发现和表征，可能会产生互补的材料类是非常感兴趣的。该项目的主要目标是探索硫族元素键合，最近定义的非共价相互作用，是否可以故意和可靠地将分子tectons组装成低密度晶体框架材料，以实现一类新的框架：硫族元素键合的有机框架，即ChOFs。模型系统中硫属元素键介导组装的经验和计算研究为合理设计永久多孔ChOF建立了一套定量指南，其拓扑结构可根据分子结构和结晶条件预测组装。这些见解导致成分层次和有序的多组分材料，在既定的框架类难以捉摸的功能。溶液相关联的研究，如NMR光谱和ITC，和DFT为基础的计算被用来量化合成tectons之间的硫族元素键合;组装框架的原子结构，其特征在于通过单晶XRD。一个廉价的和高度模块化的模型套件练习使用建模粘土和牙签开发和传播给学生的意图，教分子组装和晶体工程的核心概念。为了减少研究型大学和URM服务的PUI之间的高年级化学课程的不平等，首席研究员开发并提供了一个混合的高年级物理有机课程，同时教授面对面，该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识产权进行评估来支持。优点和更广泛的影响审查标准。