In:
Angewandte Chemie, Wiley, Vol. 135, No. 12 ( 2023-03-13)
Abstract:
We report a long‐lived charge‐separated state in a chromophoric pair ( DC‐PDI 2 ) that uniquely integrates the advantages of fundamental processes of photosynthetic reaction centers: i) Symmetry‐breaking charge‐separation (SB‐CS) and ii) Marcus‐inverted‐region dependence. The near‐orthogonal bichromophoric DC‐PDI 2 manifests an ultrafast evolution of the SB‐CS state with a time constant of =0.35±0.02 ps and a slow charge recombination (CR) kinetics with =4.09±0.01 ns in ACN. The rate constant of CR of DC‐PDI 2 is 11 686 times slower than SB‐CS in ACN, as the CR of the PDI radical ion‐pair occurs in the deep inverted region of the Marcus parabola ( 〉 λ). In contrast, an analogous benzyloxy (BnO)‐substituted DC‐BPDI 2 showcases a ≈10‐fold accelerated CR kinetics with lowering to ≈1536 in ACN, by virtue of a decreased CR driving force. The present investigation demonstrates a control of molecular engineering to tune the energetics and kinetics of the SB‐CS material, which is essential for next‐generation optoelectronic devices.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.12
DOI:
10.1002/ange.202216482
Language:
English
Publisher:
Wiley
Publication Date:
2023
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