Photoinduced ultrafast multielectron transfer and long- lived charge- accumulated state in a fullerene- indacenodithiophene dumbbell triad

• 成果类型: Article
• 署名作者: Wang, Chong; Wu, Bo; Li, Yang; Jiang, Ying; Dong, Tianyang; Zhou, Shen; Wang, Chunru; Bai, Chunli
• 署名单位: Chinese Academy of Sciences; Institute of Chemistry, CAS; Chinese Academy of Sciences; University of Chinese Academy of Sciences, CAS; Beijing University of Posts & Telecommunications; National University of Defense Technology - China
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-10402
• DOI: 10.1073/pnas.2414671121
• 发表日期: 2024-12-10
• 关键词: separation; c-60; recombination; chemistry; ring

摘要

Photoinduced ultrafast multielectron transfer (m- ET) and long- lived charge- accumulated states in single molecules hold promise for light- energy conversion and utilization. However, compared to single- electron transfer (s- ET), m- ET tends to be thermodynamically and kinetically unfavorable. Here, we construct a dumbbell- shaped fullerene- indacenodithiophene triad, IT2, modified with two C 60 units in the donor indacenodithiophene. Exciting the C 60 units, ultrafast m- ET occurs with a time constant of 0.5 ps, accumulating two holes with a lifetime of 10 mu s. Benefitting from a larger driving force, lower reorganization energy, and smaller structural changes, the rate of m- ET is 23 times faster than that of s- ET, and the lifetime of the m- ET product is 1.4 x 105 times longer than that of the s- ET products. These attributes endow IT2 with superior photocatalytic performance in multielectron oxidation reactions. This is an instance of achieving faster m- ET and a longer m- ET product lifetime than s- ET in a single molecule. This finding provides unique insights for the construction and application of intramolecular m- ET and charge accumulation systems in photocatalysis and molecular devices.