دورية أكاديمية
Controlling Symmetry Breaking Charge Transfer in BODIPY Pairs.
| العنوان: | Controlling Symmetry Breaking Charge Transfer in BODIPY Pairs. |
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| المؤلفون: | Estergreen L; Department of Chemistry, University of Southern California, Los Angeles California 90089, United States., Mencke AR; Department of Chemistry, University of Southern California, Los Angeles California 90089, United States., Cotton DE; Department of Chemistry, University of Texas at Austin, Austin Texas 78712, United States., Korovina NV; Department of Chemistry, University of Colorado Boulder, Boulder, Colorado 80309, United States., Michl J; Department of Chemistry, University of Colorado Boulder, Boulder, Colorado 80309, United States., Roberts ST; Department of Chemistry, University of Texas at Austin, Austin Texas 78712, United States., Thompson ME; Department of Chemistry, University of Southern California, Los Angeles California 90089, United States., Bradforth SE; Department of Chemistry, University of Southern California, Los Angeles California 90089, United States. |
| المصدر: | Accounts of chemical research [Acc Chem Res] 2022 Jun 07; Vol. 55 (11), pp. 1561-1572. Date of Electronic Publication: 2022 May 23. |
| نوع المنشور: | Journal Article; Research Support, U.S. Gov't, Non-P.H.S. |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 0157313 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-4898 (Electronic) Linking ISSN: 00014842 NLM ISO Abbreviation: Acc Chem Res Subsets: MEDLINE |
| أسماء مطبوعة: | Original Publication: Washington, American Chemical Society. |
| مواضيع طبية MeSH: | Photosynthesis* , Solar Energy*, Boron Compounds ; Catalysis ; Sunlight |
| مستخلص: | Symmetry breaking charge transfer (SBCT) is a process in which a pair of identical chromophores absorb a photon and use its energy to transfer an electron from one chromophore to the other, breaking the symmetry of the chromophore pair. This excited state phenomenon is observed in photosynthetic organisms where it enables efficient formation of separated charges that ultimately catalyze biosynthesis. SBCT has also been proposed as a means for developing photovoltaics and photocatalytic systems that operate with minimal energy loss. It is known that SBCT in both biological and artificial systems is in part made possible by the local environment in which it occurs, which can move to stabilize the asymmetric SBCT state. However, how environmental degrees of freedom act in concert with steric and structural constraints placed on a chromophore pair to dictate its ability to generate long-lived charge pairs via SBCT remain open topics of investigation.In this Account, we compare a broad series of dipyrrin dimers that are linked by distinct bridging groups to discern how the spatial separation and mutual orientation of linked chromophores and the structural flexibility of their linker each impact SBCT efficiency. Across this material set, we observe a general trend that SBCT is accelerated as the spatial separation between dimer chromophores decreases, consistent with the expectation that the electronic coupling between these units varies exponentially with their separation. However, one key observation is that the rate of charge recombination following SBCT was found to slow with decreasing interchromophore separation, rather than speed up. This stems from an enhancement of the dimer's structural rigidity due to increasing steric repulsion as the length of their linker shrinks. This rigidity further inhibits charge recombination in systems where symmetry has already enforced zero HOMO-LUMO overlap. Additionally, for the forward transfer, the active torsion is shown to increase LUMO-LUMO coupling, allowing for faster SBCT within bridging groups.By understanding trends for how rates of SBCT and charge recombination depend on a dimer's internal structure and its environment, we identify design guidelines for creating artificial systems for driving sustained light-induced charge separation. Such systems can find application in solar energy technologies and photocatalytic applications and can serve as a model for light-induced charge separation in biological systems. |
| المشرفين على المادة: | 0 (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) 0 (Boron Compounds) |
| تواريخ الأحداث: | Date Created: 20220523 Date Completed: 20220608 Latest Revision: 20220721 |
| رمز التحديث: | 20240628 |
| DOI: | 10.1021/acs.accounts.2c00044 |
| PMID: | 35604637 |
| قاعدة البيانات: | MEDLINE |
Find this issue from the American Chemical Society | تدمد: | 1520-4898 |
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| DOI: | 10.1021/acs.accounts.2c00044 |