Discrete π-Stacks from Self-Assembled Perylenediimide Analogues

Feng Su; Guangmei Chen; Peter A Korevaar; Fangfang Pan; Huijiao Liu; Zongxia Guo; Albertus P H J Schenning; Hui-Jun Zhang; Jianbin Lin; Yun-Bao Jiang

doi:10.1002/anie.201907838

Discrete π-Stacks from Self-Assembled Perylenediimide Analogues

Angew Chem Int Ed Engl. 2019 Oct 21;58(43):15273-15277. doi: 10.1002/anie.201907838. Epub 2019 Sep 12.

Authors

Feng Su¹, Guangmei Chen¹, Peter A Korevaar², Fangfang Pan³, Huijiao Liu¹, Zongxia Guo⁴, Albertus P H J Schenning⁵, Hui-Jun Zhang¹, Jianbin Lin^{1

6}, Yun-Bao Jiang^{1

6}

Affiliations

¹ Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
² Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525, AJ, Nijmegen, The Netherlands.
³ College of Chemistry, Central China Normal University, Wuhan, 430079, P. R. China.
⁴ College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, P. R. China.
⁵ Department of Chemical Engineering and Chemistry, Stimuli-responsive Functional Materials and Devices, Eindhoven University of Technology, Den Dolech 2, 5612, AZ, Eindhoven, The Netherlands.
⁶ MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, Xiamen University, Xiamen, 361005, P. R. China.

PMID: 31436902
DOI: 10.1002/anie.201907838

Abstract

The formation of well-defined finite-sized aggregates represents an attractive goal in supramolecular chemistry. In particular, construction of discrete π-stacked dye assemblies remains a challenge. Reported here is the design and synthesis of a novel type of discrete π-stacked aggregate from two comparable perylenediimide (PDI) dyads (PEP and PBP). The criss-cross PEP-PBP dimers in solution and (PBP-PEP)-(PEP-PBP) tetramers in the solid state are well elucidated using single-crystal X-ray diffraction, dynamic light scattering, and diffusion-ordered NMR spectroscopy. Extensive π-π stacking between the PDI units of PEP and PBP as well as repulsive interactions of swallow-tailed alkyl substituents are responsible for the selective formation of discrete dimer and tetramer stacks. Our results reveal a new approach to preparing discrete π stacks that are appealing for making assemblies with well-defined optoelectronic properties.

Keywords: chirality; noncovalent interactions; self-assembly; structure elucidation; supramolecular structures.

Grants and funding

21772162, 21772165, 21572188, 21573118/Natural Science Foundation of China