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

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）是由有机分子连接的金属离子或簇组成的结晶纳米多孔材料，由于其精确控制的纳米环境和合成可调性，MOF已成为一类有前途的可调节材料。然而，MOF 的绝缘性质限制了它们在需要电荷传输的技术中的使用，例如电子学。该项目由该部门的固态和材料化学项目支持。 NSF 的材料研究建立在 Marinescu 小组之前的研究基础上，该研究表明一些二维扩展框架表现出高电导率，通过表征和研究，加深了对控制这些框架传输特性的因素的理解。改变电子环境，以及研究这些 MOF 的整体特性，这些框架的合成可调节性可以对其配位环境进行出色的控制，从而促进了结构-活性研究，该奖项的教育部分整合了与化学相关的方面。能源和材料实验室研究的应用程序覆盖中/高中学生和教师，以及博士后学者、研究生和本科生，重点关注女性这一科学界代表性不足的群体。技术摘要：该项目由NSF 材料研究部的固态和材料化学项目研究了氧化还原活性配体（如二硫烯）的使用，作为促进 MOF 电荷传输的一种手段，Marinescu 小组先前的研究已经证明。基于苯六硫醇盐和2,3,6,7,10,11-三亚苯基六硫醇盐配体的二维含钴MOFs可以产生具有高结晶度的这些含有金属和配体轨道的广泛离域的MOFs表现出高电性。电导率，该项目测试了 PI 的基本假设，即 MOF 的传输特性可以通过合成的、自下而上的方法进行调节重点是调整配位球效应以及将客体物种和掺杂剂纳入这些多孔结构中，以了解促进和控制这些 MOF 的电子环境的潜在结构特征和机制。提出的 MOF 是通过改变金属中心的特性、氧化态和电荷补偿阳离子来调节的。这些研究提供了有关局部环境和金属二硫醇骨架的整体特性如何影响其的信息。导电性，这有助于制定导电 MOF 的设计原则。与该奖项相关的教育活动是多方面的，涉及洛杉矶中/高中学生和教师，以及南加州大学的研究生和本科生：PI。 (1) 领导一项针对本科生的女性辅导计划，以增加女性对科学的参与；(2) 为当地学校的教师举办暑期研讨会，进行实践实验，最重要的是，参与这些实验的学生。发展持久的努力文化该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Hydrogen Evolving Activity of Dithiolene-Based Metal–Organic Frameworks with Mixed Cobalt and Iron Centers

钴铁混合中心二硫醇基金属有机骨架的析氢活性

• DOI: 10.1021/acs.inorgchem.1c00900
• 发表时间: 2021-08
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Chen, Keying;Downes, Courtney A.;Goodpaster, Jason D.;Marinescu, Smaranda C.
• 通讯作者: Marinescu, Smaranda C.

Electronically-coupled redox centers in trimetallic cobalt complexes

三金属钴配合物中的电子耦合氧化还原中心

• DOI: 10.1039/d1dt03404a
• 发表时间: 2022-04
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Intrator, Jeremy A.;Orchanian, Nicholas M.;Clough, Andrew J.;Haiges, Ralf;Marinescu, Smaranda C.
• 通讯作者: Marinescu, Smaranda C.