期刊
NATURE CHEMISTRY
卷 14, 期 7, 页码 786-+出版社
NATURE PORTFOLIO
DOI: 10.1038/s41557-022-00927-y
关键词
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资金
- US Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-FG02-99ER14999]
- National Science Foundation Graduate Research Fellowship Program [DGE-1842165]
- Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource [NSF ECCS-2025633]
- State of Illinois
- International Institute for Nanotechnology (IIN)
- Northwestern University
Understanding the photophysics and photochemistry of molecular pi-stacked chromophores is crucial for their utilization as functional photonic materials. This study compares the excited-state dynamics of a covalent slip-stacked perylenediimide dimer and trimer, revealing fundamental insights into electronic state mixing and symmetry-breaking charge separation beyond the dimer limit.
Understanding the photophysics and photochemistry of molecular pi-stacked chromophores is important for utilizing them as functional photonic materials. However, these investigations have been mostly limited to covalent molecular dimers, which can only approximate the electronic and vibronic interactions present in the higher oligomers typical of functional organic materials. Here we show that a comparison of the excited-state dynamics of a covalent slip-stacked perylenediimide dimer (2) and trimer (3) provides fundamental insights into electronic state mixing and symmetry-breaking charge separation (SB-CS) beyond the dimer limit. We find that coherent vibronic coupling to high-frequency modes facilitates ultrafast state mixing between the Frenkel exciton (FE) and charge-transfer (CT) states. Subsequently, solvent fluctuations and interchromophore low-frequency vibrations promote CT character in the coherent FE/CT mixed state. The coherent FE/CT mixed state persists in 2, but, in 3, low-frequency vibronic coupling collapses the coherence, resulting in ultrafast SB-CS between the distal perylenediimide units.
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