Conductive Dithiolene-Based Metal Organic Frameworks (MOFs) with Tunable Transport Properties

具有可调传输特性的导电二硫醇烯基金属有机框架 (MOF)

• 批准号: 2004868
• 负责人: Smaranda Marinescu
• 金额: $ 50.5万
• 依托单位: University of Southern California
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-05-01 至 2024-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2004868&HistoricalAwards=false
• 关键词: Conductive; Dithiolene; Based; Metal; Organic; Conductive; Dithiolene; Based; Metal; Organic

Non-technical abstract: Metal-organic frameworks (MOFs) are crystalline nanoporous materials composed of metal ions or clusters linked by organic molecules. Due to their precisely controlled nano-enviroments and synthetic tunability, MOFs have emerged as a promising class of materials with adjustable properties However, the insulating nature of MOFs has limited their use in technologies that require charge transport, such as electronics. This project, which is supported by the Solid State and Materials Chemistry Program in the Division of Materials Research at NSF, builds on previous research in the Marinescu group that has shown that some two-dimensional extended frameworks display high electrical conductivity. With this award, the understanding of the factors that govern the transport properties of these frameworks is advanced by characterizing and changing the electronic environment, as well as studying the bulk properties of these MOFs. The synthetic tunability of these frameworks allows for excellent control of their coordination environment, which facilitates structure-activity studies. The educational components of this award integrate aspects of chemistry related to energy and materials applications researched in the laboratory and reach middle/high school students and teachers, as well as postdoctoral scholars, graduate, and undergraduate students, with a focus on women, an underrepresented group in science.Technical abstract: With this project, which is supported by the Solid State and Materials Chemistry Program in the Division of Materials Research at NSF, the use of redox active ligands, such as dithiolenes, is investigated as a means to facilitate charge transport through MOFs. Previous research in the Marinescu group has demonstrated that two-dimensional cobalt-containing MOFs based on benzenehexathiolate and 2,3,6,7,10,11-triphenylenehexathiolate ligands can be produced with high degree of crystallinity. These MOFs that contain extensive delocalization of the metal and ligand orbitals exhibit high electrical conductivity, and this project tests the PI’s fundamental hypothesis that the transport properties of MOFs can be modulated through a synthetic, bottom-up approach with an emphasis on tuning the coordination sphere effects and incorporation of guest-species and dopants into these porous architectures. Several structurally analogous frameworks are investigated to understand the underlying structural features and mechanisms, which promote and control the conductivity of these MOFs. The electronic environment of these proposed MOFs are modulated by changing the identity of the metal center, its oxidation state, and charge compensating cations. The studies provide information on how the local environment and the bulk properties of the metal dithiolene frameworks affect their conductivity, which is instrumental in the development of design principles to generate conductive MOFs. The educational activities associated with this award are multifaceted and involve Los Angeles middle/high-school students and teachers, as well as graduate and undergraduate students from USC: the PI (1) leads a mentoring program for women at the undergraduate level to increase the participation of women in science; and (2) develops a summer workshop for teachers from local schools where hands-on experiments are performed. Most importantly, students involved in these efforts develop a long-lasting culture of contributing to their scientific and non-scientific communities.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.

非技术摘要：金属有机框架（MOF）是由金属离子或有机分子链接的簇组成的结晶纳米多孔材料。由于其精确控制的纳米磁性和合成可线性性，MOF已成为具有可调节性能的材料的承诺类别类别，但是，MOF的绝缘性质限制了其在需要电荷传输的技术中的使用，例如电子设备。该项目得到了NSF材料研究部的固态和材料化学计划的支持。有了这个奖项，通过表征和改变电子环境以及研究这些MOF的批量特性来提出对控制这些框架运输特性的因素的理解。这些框架的综合可密钉性可以很好地控制其协调环境，这些环境的结构活性研究。该奖项的教育组成部分整合化学方面与在实验室和中学/高中生和教师中所研究的能源和材料应用有关的方面研究活性配体，例如二硫醇，是一种促进通过MOF的电荷运输的手段。 MarinesCU组的先前研究表明，基于苯二硫代硫酸盐的二维MOF和2,3,6,7,10,11-1111-三苯基二苯乙二苯乙烯配体可以具有很高的结晶度。这些MOF包含金属和配体轨道的广泛离域化，暴露了高电导率，该项目测试了PI的基本假设，即可以通过合成的，自下而上的方法来调制MOF的运输特性，重点是将协同效应和辅助型物种的配位效果和企业调整为这些杂货和企业，以使这些特色和构造型物质进行调整。研究了几个结构类似的框架，以了解促进和控制这些MOF的电导率的潜在结构特征和机制。这些提出的MOF的电子环境通过改变金属中心的身份，其氧化状态和电荷补偿阳离子来调节。这些研究提供了有关金属二硫烯框架的本地环境和块状特性如何影响其电导率的信息，这对生成导电性MOF的设计原理具有重要作用。与该奖项相关的教育活动是多方面的，涉及洛杉矶中学/高中生和老师，以及来自USC的研究生和本科生：PI（1）领导一项在本科级别的女性心理计划，以增加女性参与科学的参与； （2）为来自当地学校的教师开发了一个夏季研讨会，在那里进行了动手实验。最重要的是，参与这些努力的学生开发了一种持久的文化，为他们的科学和非科学社区做出了贡献。该奖项反映了NSF的法定使命，并通过使用基金会的知识分子和更广泛的影响评估标准来评估，被认为是珍贵的支持。