Unequal Perylene Diimide Twins in a Quadruple Assembly |
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| Authors: | Shuqi Chen Shishi Feng Albert J. Markvoort Cankun Zhang Enyang Zhou WanZhen Liang Hui-Jun Zhang Yun-Bao Jiang Jianbin Lin |
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| Affiliation: | 1. Department of Chemistry, College of Chemistry and Chemical Engineering, MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, Xiamen University, Xiamen, 361005 P. R. China;2. State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 P. R. China;3. Computational Biology Group and Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (The, Netherlands;4. Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, 361005 P. R. China;5. School of Mathematical Sciences, Xiamen University, Xiamen, 361005 P. R. China |
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| Abstract: | 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 ( POP s) 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. |
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| Keywords: | Coupling Discrete Stacking Light Harvesting Perylene Diimide Unequal Assembly |
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