CAS: New BODIPYs That Are Capable to Form Coordination-bonded Panchromatic Arrays For Light-harvesting

CAS：能够形成用于光捕获的配位键合全色阵列的新型 BODIPY

• 批准号: 2153081
• 负责人: Viktor Nemykin
• 金额: $ 39.13万
• 依托单位: University of Tennessee Knoxville
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-08-01 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2153081&HistoricalAwards=false
• 关键词: CAS; New; BODIPYs; Capable; Form

With the support of the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) Program in the Division of Chemistry, Professor Victor Nemykin of the University of Tennessee is studying several new classes of molecules, that have the potential to replace currently used carbon nanomaterials as electron acceptors in the light-harvesting modules of organic photovoltaics (OPV) devices. Naturally occurring porphyrins and their derivatives are well-known "pigments of life," which are responsible for light-harvesting, oxygen transfer, the catalytic transformation of biological substrates, and many other functions. Porphyrin derivatives perform best in Dye-Sensitized Solar Cell (DSSC) modules. Although fullerene, its derivatives, and the other nano-carbon materials are typically thought of as electron-acceptors for donor-acceptor assemblies, they suffer several limitations. First, they are not bright chromophores, especially for the low-energy range of the solar spectrum. Second, over the years, it has become clear that they significantly limit the mechanical flexibility, stability, and overall performance of OPV cells. Finally, fullerene and its derivatives are still very expensive when the overall cost of the OPV device is considered. In order to address the major deficiencies of fullerenes and their derivatives, Professor Nemykin’s team is planning to prepare a broad range of bright porphyrin-related chromophores with a first reduction potential that is energetically close to that of fullerenes (electron-donors) paired with a set of non-fullerene, BODIPY-like electron acceptors. They hope that these new molecules will outperform currently used nano-carbon materials as electron acceptors in OPV devices to eventually allow for the development of new, economically viable light-harvesting modules for solar cells. This project will help to train next generation research scientists through the cross-disciplinary nature of the research, with exposure to inorganic, organometallic and theoretical chemistry, as well significant application of spectroscopy. In an effort to reduce the manufacturing cost of OPV solar cells, researchers have been developing new OPV technologies that adopt room temperature solution-based fabrication techniques. The resulting solar cells also have many potential advantages in terms of mechanical properties (flexible solar cells) and broad platform deployment (paint-on solar cells). In pursuit of the preparation of the artificial light-harvesting materials that would be as effective as the natural photosystem, a variety of synthetic dyes such as porphyrins, phthalocyanines, and BODIPYs been studied in the last decade, with the best, porphyrin-based, DSSC system providing ~13.5% efficiency in the solar light-to-electricity conversion. In this project, the principal investigator’s team will prepare, characterize, and investigate a set of new panchromatic supramolecular assemblies formed using coordinating bonds between electron-donating porphyrinoids and new electron-accepting chromophores. In particular, specific emphasis will be on the design, preparation, and characterization of the new electron-deficient chromophores that can outperform and substitute nano-carbon materials as electron-acceptors. These new chromophores will belong to the electron-deficient BODIPY family including aza-BODIPYs, and MB-DIPYs. Photo-induced electron-transfer processes between porphyrinoids (electron-donors) and new electron-acceptors (BODIPYs, aza-BODIPYs, and MB-DIPYs) in supramolecular assemblies will be studied by an array of the experimental and theoretical methods to characterize these systems thoroughly and identify optimal non-fullerene donor-acceptor systems for eventual deployment in OPV devices.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.

在化学系化学结构，动力学和机制B（CSDM-B）计划的支持下，田纳西大学的维克托·内米金教授正在研究几种新的分子，这些分子有可能取代目前使用的碳纳米材料作为有机光生物学（OPV）设备的光捕获模块中的电子受体。天然存在的卟啉及其衍生物是众所周知的“生命色素”，其负责光捕获、氧转移、生物底物的催化转化以及许多其他功能。卟啉衍生物在染料敏化太阳能电池（DSSC）模块中表现最好。虽然富勒烯、其衍生物和其他纳米碳材料通常被认为是供体-受体组装体的电子受体，但它们受到一些限制。首先，它们不是明亮的发色团，特别是在太阳光谱的低能区。其次，多年来，已经清楚的是，它们显著限制了OPV电池的机械柔性、稳定性和整体性能。最后，当考虑OPV器件的总成本时，富勒烯及其衍生物仍然非常昂贵。为了解决富勒烯及其衍生物的主要缺陷，Nemykin教授的团队计划制备一系列明亮的卟啉相关发色团，其第一还原电位在能量上接近富勒烯（电子供体）与一组非富勒烯，BODIPY类电子受体配对。他们希望这些新分子将优于目前使用的纳米碳材料作为OPV器件中的电子受体，最终允许开发新的、经济上可行的太阳能电池捕光模块。该项目将通过研究的跨学科性质，接触无机，有机金属和理论化学以及光谱学的重要应用，帮助培养下一代研究科学家。 为了降低OPV太阳能电池的制造成本，研究人员一直在开发采用室温溶液制造技术的新OPV技术。由此产生的太阳能电池在机械性能（柔性太阳能电池）和广泛的平台部署（涂敷太阳能电池）方面也具有许多潜在的优势。为了追求与天然光系统一样有效的人工光捕获材料的制备，在过去十年中研究了各种合成染料，如卟啉、酞菁和BODIPY，其中最好的基于卟啉的DSSC系统在太阳能光电转换中提供约13.5%的效率。在这个项目中，主要研究者的团队将准备，表征和研究一组新的全色超分子组装体，这些组装体是使用电子给体卟啉和新的电子接受发色团之间的配位键形成的。特别是，具体的重点将放在新的缺电子发色团的设计，制备和表征，可以优于和替代纳米碳材料作为电子受体。这些新的发色团将属于缺电子BODIPY家族，包括氮杂-BODIPY和MB-DIPY。卟啉类化合物间的光诱导电子转移过程（电子供体）和新电子受体（BODIPY，氮杂-BODIPY，和MB-DIPY）在超分子组装将研究的实验和理论方法的阵列，以彻底表征这些系统，并确定最佳的非富勒烯供体-该奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的学术价值和更广泛的影响审查标准。

项目成果

Radical Complexes of Nickel(II)/Copper(II) and Redox Non‐innocent MB‐DIPY Ligands: Unusual Stability and Strong Near‐Infrared Absorption at λ max ∼1300 nm

镍 (II)/铜 (II) 和氧化还原非无害 MB-DIPY 配体的自由基配合物：异常的稳定性和强近红外吸收（在 最大 ≤1300 nm 处）

• DOI: 10.1002/chem.202201181
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: Zatsikha, Yuriy V.;Shamova, Liliya I.;Shepit, Michael;Berry, Steven M.;Thomas, Fabrice;Herbert, David E.;van Lierop, Johan;Nemykin, Victor N.
• 通讯作者: Nemykin, Victor N.

Meso ‐Carbon Atom Nucleophilic Attack Susceptibility in the Sterically Strained Antiaromatic Bis‐BODIPY Macrocycle and Extended Electron‐Deficient BODIPY Precursor**

空间应变反芳香族双 BODIPY 大环和扩展电子中的内消旋碳原子亲核攻击敏感性 - 缺陷 BODIPY 前体**

• DOI: 10.1002/chem.202201261
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: Zatsikha, Yuriy V.;Schrage, Briana R.;Blesener, Tanner S.;Harrison, Laurel A.;Ziegler, Christopher J.;Nemykin, Victor N.
• 通讯作者: Nemykin, Victor N.

Transient Absorption Spectra of Metal‐Free and Transition‐Metal 5,10,15,20‐Tetraferrocene Porphyrins: Influence of the Central Metal Ion, Solvent Polarity, and the Axial Ferrocene Ligand

金属—游离态和过渡态—金属 5、10、15、20—四二茂铁卟啉的瞬态吸收光谱：中心金属离子、溶剂极性和轴向二茂铁配体的影响

• DOI: 10.1002/ejic.202101007
• 发表时间: 2022
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Schrage, Briana R.;Ermilov, Eugeny;Nemykin, Victor N.
• 通讯作者: Nemykin, Victor N.

Outsourcing Intersystem Crossing without Heavy Atoms: Energy Transfer Dynamics in PyridoneBODIPY–C 60 Complexes

外包无重原子的系间穿越：吡啶酮BODIPY™C 60 配合物中的能量转移动力学

• DOI: 10.1021/acs.jpclett.2c02388
• 发表时间: 2022
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Swedin, Rachel K.;Healy, Andrew T.;Schaffner, Jacob W.;Kuzmin, Ilya A.;Zatsikha, Yuriy V.;Nemykin, Victor N.;Blank, David A.
• 通讯作者: Blank, David A.