Unequal Perylene Diimide Twins in a Quadruple Assembly

Natural light‐harvesting (LH) systems can divide identical dyes into unequal aggregate states, thereby achieving intelligent “allocation of labor”. From a synthetic point of view, the construction of such kinds of unequal and integrated systems without the help of proteinaceous scaffolding is challe...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-04, Vol.62 (15), p.e202300786-n/a
Main Authors: Chen, Shuqi, Feng, Shishi, Markvoort, Albert J., Zhang, Cankun, Zhou, Enyang, Liang, WanZhen, Zhang, Hui‐Jun, Jiang, Yun‐Bao, Lin, Jianbin
Format: Article
Language:English
Subjects:
Assembly
Chromophores
Coupling
Couplings
Crystallography
Diimide
Discrete Stacking
Dyes
Light Harvesting
Magnetic resonance spectroscopy
Natural lighting
NMR
NMR spectroscopy
Nuclear magnetic resonance
Perylene Diimide
Scaffolding
Unequal Assembly
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Summary:Natural light‐harvesting (LH) systems can divide identical dyes into unequal aggregate states, thereby achieving intelligent “allocation of labor”. From a synthetic point of view, the construction of such kinds of unequal and integrated systems without the help of proteinaceous scaffolding is challenging. Here, we show that four octatetrayne‐bridged ortho‐perylene diimide (PDI) dyads (POPs) self‐assemble into a quadruple assembly (POP)4 both in solution and in the solid state. The two identical PDI units in each POP are compartmentalized into weakly coupled PDIs (P520) and closely stacked PDIs (P550) in (POP)4. The two extreme pools of PDI chromophores were unambiguously confirmed by single‐crystal X‐ray crystallography and NMR spectroscopy. To interpret the formation of the discrete quadruple assembly, we also developed a two‐step cooperative model. Quantum‐chemical calculations indicate the existence of multiple couplings within and across P520 and P550, which can satisfactorily describe the photophysical properties of the unequal quadruple assembly. This finding is expected to help advance the rational design of dye stacks to emulate functions of natural LH systems. In a quadruple assembly (POP)4, two identical perylene diimide (PDI) units in each POP are compartmentalized into weakly coupled PDIs (P520) and closely stacked PDIs (P550). The two groups of spectrally distinct PDI units provide a rapid gradient‐directed energy transfer from P520 to P550.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202300786