Crystal Engineering of Functional Materials

该方案的目的是为基于金属有机骨架(MOF)的二阶非线性光学(NLO)和新型微孔储氢固体的晶体工程开发合理的策略。固态材料的性质不仅取决于材料的结构，还取决于材料中分子构件的排列方式。我们将采用分子积木的方法来合理地合成NLO活性的晶体MOF固体和薄膜。在这种聚合物配位网络中，金属-配体连接被用来抵消不利的相互作用，并确保NLO发色团的极性取向。新型的“富含芳烃”的有机构件以及金属中心的配位不饱和性将被用来加强氢与MOF的相互作用。这项拟议的研究将探索利用自下而上的方法合成新型功能材料。拟议的研究还将整合到博士后、研究生、本科生和高中生的培训中。PI将继续从代表性不足的团体中招收本科生，并与美国化学学会的当地部门合作指导学生。因此，拟议的研究将对处于非常不同职业阶段的人员的培训产生重大影响。%拟议的研究将从根本上探索新的自下而上的方法，以合成新型功能材料。本研究的目标包括用于二阶非线性光学(NLO)的非中心对称固体的晶体工程和用于储氢的新型微孔固体的合理合成。高效的NLO材料的成功合成是未来宽带通信的关键，而储氢材料的可获得性将使基于氢的燃料电池技术能够用于移动电源。氢基燃料电池技术的发展不仅对国家能源安全至关重要，而且对减少环境污染也具有重要意义。除了对我国未来信息和能源技术的潜在影响外，拟议的研究还将促进研究和教育的促进和整合。参与拟议跨学科研究的研究生和博士后研究助理将接受培训，掌握对他们未来作为职业化学家的职业生涯至关重要的技能。国际学生联合会将继续从代表性不足的群体中招收本科生，并将与美国学生联合会的当地部门合作，指导高中生。因此，拟议的研究将对包括高中生、本科生、研究生和博士后研究助理在内的人员的培训产生重大影响。

The objective of this proposal is to develop rational strategies for the crystal engineering of polar solids based on metal-organic frameworks (MOFs) for second-order nonlinear optics (NLO) and new microporous solids for hydrogen storage. The properties of solid-state materials depend not only on the structures but also on the alignment of molecular building blocks in the bulk. A molecular building block approach will be taken to rationally synthesize NLO-active crystalline MOF solids and thin films. In such polymeric coordination networks, metal-ligand ligation is utilized to counteract unfavorable interactions and to ensure polar orientations of NLO chromophores. Novel "aromatics-rich" organic building blocks as well as coordination unsaturation of metal centers will be utilized to enhance the interactions of hydrogen with the MOF. The proposed research will explore the synthesis of novel functional materials using bottom-up approaches. The proposed research will also be integrated into the training of postdoctoral, graduate, undergraduates, and high school students. The PI will continue to recruit undergraduate students from underrepresented groups, and work with local section of the American Chemical Society to mentor students. The proposed research will thus have a significant impact on the training of the personnel at very different career stages.%%%The proposed research will explore fundamentally new bottom-up approaches towards the synthesis of novel functional materials. The goals of this research include crystal engineering of noncentrosymmetric solids for second-order nonlinear optics (NLO) and rational synthesis of new microporous solids for hydrogen storage. Successful synthesis of efficient NLO materials is key to future broadband communications, while the availability of hydrogen storage materials will enable hydrogen-based fuel cell technology for mobile power sources. The development of hydrogen-based fuel cell technology is of paramount importance not only to national energy security but also to the reduction of environmental pollution. In addition to its potential impact on our nation's future information and energy technologies, the proposed research will also advance the promotion and integration of research and education. Graduate students and postdoctoral research associates participating in the proposed interdisciplinary research will be trained with the skills that are crucial to their future careers as career chemists. The PI will continue to recruit undergraduate students from underrepresented groups, and will work with local section of ACS to mentor high school students. The proposed research will thus have a significant impact on the training of personnel, including high school students, undergraduate students, graduate students, and postdoctoral research associates.