CAREER: Molecular Building Block Approach to Zeolite-like Metal-Organic Frameworks (ZMOFs)

技术解释该项目旨在开发新的策略来设计和合成具有大的可调腔的刚性多孔材料，这些材料是由分子构建块组成的。金属-配体定向组装方法将用于将刚性定向四面体结构单元和具有公度几何结构的有机连接物排列成具有大空穴的扩展的沸石状金属有机骨架(ZMOF)。所提出的多孔ZMOF是典型的具有离子交换能力的阴离子，这一性质在形式上只在无机沸石中才能看到，而在传统的MOF中很少见。它们的杂化性质和超大的空腔表明它们可能在与大分子实体有关的应用中有用，在那里纯无机沸石是无效的。由此产生的设计原则将为将分子结构和功能纳入扩展固态材料铺平道路。这些结果有望帮助开发具有其他功能的材料，如手性分离、大分子分离、选择性催化和主客体化学。这项工作将作为培训学生尖端固态材料合成和表征技术的媒介。此外，还启动了教师研究经验方案和本科生学术研究经验方案，这将扩大拟议工作的影响。这项工作的范围将有助于面向不同的本科生和预科教师群体进行教育，以促进高等教育，提高研究意识，并产生广泛的社会影响。非技术解释环境技术、超级催化剂、手性分离和天然气储存等领域的技术进步主要取决于新材料的发现，以及现有材料的改进。人们越来越意识到并迫切需要制定合理的策略来设计和合成具有特定和可调功能的材料。从分子构建块(MBBS)构建固态材料的能力为实现这一目标提供了巨大的潜力。该项目研究了从MBBS设计和合成具有大而可调的腔的硬质多孔材料的新策略，评估它们的潜在应用，并将它们整合到教育宣传中。合理组装和制备具有易于功能化的大空腔的多孔材料具有特殊的科学和技术价值，并为大分子、纳米技术、光学、传感器、医学等领域的创新应用提供巨大的潜力。该研究所将参与教师研究体验，通过让教师参与从大学到当地初中/高中的知识转移，帮助沟通大学预科学校和大学，并为本科生发起学术研究体验，鼓励本科生通过在其学术生涯的早期阶段参与研究经验来继续研究生学习。参与这个跨学科项目的学生将接受材料合成和表征方面的各种先进技术的培训，为他们的工业和学术生涯做好准备。

TECHNICAL EXPLANATIONThis project aims to develop novel strategies for design and synthesis of rigid porous materials with large and tunable cavities from molecular building blocks. A metal-ligand directed assembly approach will be used to order rigid directional tetrahedral building units and organic linkers with commensurate geometries into expanded zeolite-like metal-organic frameworks (ZMOFs) possessing large cavities. The proposed porous ZMOFs are typically anionic with ion exchange capacity, a property formally only seen in inorganic zeolites and rare in conventional MOFs. Their hybrid nature and extra-large cavities suggest they may be useful in applications pertaining to large molecular entities, where purely inorganic zeolites are ineffective. The resulting design principles will pave the way for the incorporation of molecular structure and functionality into extended solid-state materials. The results are anticipated to aid in developing materials with additional functions such as chiral separation, separation of large molecules, selective catalysis, and host-guest chemistry. The work will serve as a medium to train students in cutting-edge solid-state materials synthesis and characterization techniques. Furthermore, Research Experience for Teachers and Academic Research Experience for Undergraduates programs have been initiated and will broaden the impact of the proposed work. The scope of the work will aid in educational outreach toward a diverse group of undergraduate students and pre-college teachers in order to promote advanced education, increase research awareness and achieve broad societal impacts.NON-TECHNICAL EXPLANATIONTechnological advances in areas such as environmental technologies, super-catalysts, chiral separations, and gas storage depend primarily on the discovery of novel materials, as well as the enhancement of existing materials. There is a mounting consciousness and pressing need to develop logical strategies toward design and synthesis of materials with specific and tunable functions. The ability to construct solid-state materials from molecular building blocks (MBBs) offers great potential toward this objective. This project investigates novel strategies for the design and synthesis of rigid porous materials having large and tunable cavities, from MBBs, their evaluation for potential applications, and their integration into educational outreach. Rational assembly and preparation of porous materials with accessible large cavities that are readily functionalized is of exceptional scientific and technological interest, and offers great potential for innovative applications pertaining to large molecules, nanotechnology, optics, sensors, medicine, etc. The PI will participate in Research Experience for Teachers to help bridge pre-college schools and universities by involving teachers in knowledge transfer from the university to local middle/high schools, and has initiate Academic Research Experience for Undergraduates to encourage undergraduates to pursue graduate studies by engaging them in research experiences at the early stages of their academic careers. Students involved in this interdisciplinary project will be trained in a variety of advanced techniques in materials synthesis and characterization preparing them for industrial and academic careers.