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.

该奖项的全部或部分资金根据《2021 年美国救援计划法案》（公法 117-2）提供。 非技术摘要：新材料的发现给我们的社会带来了巨大的进步。这些进步通常是通过材料的两个关键组成部分之一的突破来实现的：重复的单个分子或原子构建块或单个组件的连接方式。这种材料可以被认为类似于砖墙，砖块作为重复的块，并且砂浆将它们连接在一起。虽然已知的构建块有多种多样，但只有少数已建立的连接模式存在。一般来说，每种不同的连接模式都允许创建全新的材料类别。也许最好的例子是纳米多孔框架领域，它是含有比单个分子稍大的空隙的海绵状材料。包含相似砖块但通过不同砂浆连接的纳米多孔框架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。在材料研究部固态和材料化学项目的支持下，首席研究员及其研究小组开发了一种新型纳米多孔框架，该框架由最近发现的连接模式实现。在此过程中，首席研究员增进了我们对材料连通性的了解，特别是通过增进对这种新生连通性的理解，实现了材料中无与伦比的结构复杂性，并开发了一类具有迄今为止未见的特性的材料。为了帮助教授积木如何组装成材料的核心概念，研究人员还开发并传播了一种廉价且高度模块化的模型套件练习。这款适合关卡的游戏使用多色粘土和牙签来教学生砖块和砂浆如何共同形成材料。为了减少研究型大学和主要为 URM 本科院校 (PUI) 服务的高年级化学课程之间的不平等，首席研究员开发并提供混合高年级物理有机课程，该课程同时在科罗拉多矿业学院面对面授课，并向科罗拉多州各地机构的学生远程授课。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。也许没有什么材料家族比合成多孔框架更能体现这一点，其中给定子类的特性和效用在很大程度上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，可能产生互补材料类别的分子间组装替代模式的发现和表征引起了人们的极大兴趣。该项目的主要目标是探索硫属键合（一种最近定义的非共价相互作用）是否可以有意且可靠地将分子构造组装成低密度晶体骨架材料，从而实现一类新的骨架：硫属键合有机骨架，即ChOF。模型系统中硫族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，其拓扑根据分子构造结构和结晶条件预测组装。这些见解导致了成分分层和有序的多组分材料，以及已建立的框架类别中难以捉摸的特征。溶液相关联研究（例如核磁共振波谱和 ITC）以及基于 DFT 的计算用于量化合成构造之间的硫属元素键合；组装框架的原子结构通过单晶 XRD 进行表征。开发了一种使用建模粘土和牙签的廉价且高度模块化的模型套件练习并向学生传播，旨在教授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 之间在高年级化学课程中的不平等，首席研究员开发并提供了混合高年级物理有机课程，该课程同时在科罗拉多矿业学院面对面授课，并向科罗拉多州各地机构的学生远程授课。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力优势进行评估，被认为值得支持。 以及更广泛的影响审查标准。