Crystalline Encapsulants and Functional Materials Through Molecular Design

技术综述：很少有有机固态体系能够系统和精确地操纵晶体结构和晶格度量，并预测结构结果，这对分子基功能材料的设计和合成至关重要。然而，基于二维胍-磺酸盐(GS)片层的氢键骨架已被证明是晶体工程中的基准。由于它们的结构坚固性，允许在选定的框架结构中方便地交换分子组成，通常可以通过直接的经验原理进行预测和控制。GS系统的多功能性将被用于(I)从形成分子篮的杯芳烃四磺酸盐库中合成新类别的GS主机，所述新型GS主机能够将客体分子包括在杯芳烃内而不是在相对的GS片之间的走廊区域内，(Ii)检查各种杯芳烃四磺酸盐的吸氢特性，(Iii)探索与嵌入悬浮杯芳烃中的极性客体相关的铁电行为，(Iv)以激光染料为客体的GS通道包合物，旨在调节染料的聚集状态及其相应的发射特性，(V)具有有机氮氧化物客体的GS通道包合物，旨在解开一类新型分子磁体的结构-性质关系，(Vi)手性有机单磺酸主体的对映选择性包结，(Vii)基于相对杯芳烃单元之间互补氢键间隔的离散分子胶囊的合成。构建具有光学、电子、磁性和存储性能的设计型材料，可以通过交换分子组件来系统地调节这些材料，这是通过更传统的方法难以实现的。因此，这些材料有可能影响几项美国技术，包括数据存储、通信、能源、健康和特种化学品，包括制药材料。此外，该项目将提供STEM方面的教育和研究培训，同时通过以下方式培养下一代科学家和工程师：(I)通过与纽约大学材料研究科学与工程中心和本科生研究经验网站的联系，为少数族裔服务和四年制院校的本科生和教职员工提供暑期研究经验；(Ii)为来自纽约市不同学校(包括斯宾塞学校)的高中生和纽约市K-12全女生机构的高中生提供研究经验；(Iii)为参加纽约大学化学科学硕士高中教育工作者计划的高中教师开发课程。从而加强美国最大和最多样化的学校体系的科学教育；(Iv)通过创建东北固态化学研讨会，提高学生和博士后的技能和信心，提供学生和博士后的专业发展；(Vi)通过直接的研究合作，向来自美国和国际的工业实验室和其他学术机构的科学家展示研究生和博士后。

TECHNICAL SUMMARY:Few organic solid-state systems are amenable to systematic and precise manipulation of crystal architecture and lattice metrics with predictable structural outcomes, which is crucial for the design and synthesis of molecular-based functional materials. Hydrogen-bonded frameworks based on the two-dimensional guanidinium-sulfonate (GS) sheet, however, have proven to be a benchmark in ?crystal engineering? owing to their structural robustness, which permits facile interchange of molecular constituents in selected framework architectures that often can be predicted and controlled through straightforward empirical principles. The versatility of the GS system will be exploited for (i) the synthesis of new class of GS hosts derived from a library of calixarene tetrasulfonates that form molecular baskets, suspended from the GS sheet, capable of including guest molecules within the calixarene rather than within the gallery regions between opposing GS sheets, (ii) examination of the hydrogen sorption characteristics of various guanidinium calixarenetetrasulfonates, (iii) the exploration of ferroelectric behavior associated with polar guests embedded within the suspended calixarenes, (iv) GS channel inclusion compounds with laser dyes as guests, aimed at regulating of the aggregation states of the dyes and their corresponding emission characteristics, (v) GS channel inclusion compounds with organic nitroxide guests, aimed at unraveling structure-property relationships in a new class of molecular magnets, (vi) enantioselective inclusion by chiral organomonosulfonate hosts, (vii) synthesis of discrete molecular capsules based on complementary hydrogen-bonding spacers between opposing calixarene units.NON-TECHNICAL SUMMARY:This project aims to capitalize on molecules that can be used as ?tinkertoys? to construct designer materials with optical, electronic, magnetic and storage properties that can be tuned systematically through swapping of the molecular components, which is difficult to achieve through more conventional routes. As such, these materials have to potential to impact several U.S. technologies, including data storage, communications, energy, health, and specialty chemicals, including pharmaceutical materials. Additionally, the project will provide education and research training in STEM while cultivating the next generation of scientists and engineers through (i) summer research experiences for undergraduates and faculty from minority-serving and four-year institutions through connections to the NYU Materials Research Science and Engineering Center and a Research Experiences for Undergraduates site, (ii) research experiences for high school students from various NYC schools, including the Spence School, and all-girls K-12 institution in NYC, (iii) development of courses for high school teachers enrolled in the NYU Chemistry Masters of Science for High School Educators program, thus enhancing science education in the largest and most diverse school system in the U.S., (iv) offer professional development of student and postdocs through the creation of a Northeast Solid State Chemistry Symposium that will elevate their skills and confidence in scientific presentations, (vi) expose graduate students and postdocs to scientists from industrial laboratories and other academic institutions, U.S. and international through direct research collaborations.