Homogeneous and Heterogeneous Self‐Assembly of Luminescent Pyromellitic Dianhydride‐Based Charge‐Transfer Complexes

Author:

Zhang Lulu1,Feng Zuofang1,Zhang Hongli2,Zhang Yu3,Zou Gang2,Zhang Chuang3,Lei Yilong1ORCID

Affiliation:

1. Department of Chemistry School of Science Tianjin University Tianjin 300072 P. R. China

2. CAS Key Laboratory of Soft Matter Chemistry Department of Polymer Science and Engineering iChEM University of Science and Technology of China Hefei 230026 P. R. China

3. Key Laboratory of Photochemistry Beijing National Laboratory for Molecular Sciences Institute of Chemistry Chinese Academy of Sciences Beijing 100190 P. R. China

Abstract

AbstractUsing easily hydrolyzable brominated pyromellitic dianhydride (PMDA) as an electron acceptor, a wide variety of structurally stable binary organic charge‐transfer (CT) microcrystals that are stabilized by dominant intermolecular CT interactions is achieved. By varying the electron‐donating abilities of π‐electron compounds, the resulting single crystalline CT assemblies display tailorable fluorescence emissions spanning from green to near‐infrared. Upon implantation of a π‐electron donor anthracene (An) into fluoranthene‐PMDA (Fl‐PMDA), red and NIR emissions of ternary alloyed assemblies are substantially enhanced due to efficient energy transfer from Fl‐PMDA to An‐PMDA as well as structural complementarity between two CT complexes. Depending on the well‐matched epitaxial relationship, seeded growth of phenanthrene‐PMDA (Ph‐PMDA) onto the pre‐existing An‐PMDA microcrystals is also achieved, leading to core‐shell heterostructures with full and partial coverage. Such an epitaxial growth strategy is also applicable to the construction of microscale heterostructures of diverse CT complex combinations. The ternary Fl1−xAnx‐PMDA alloyed assemblies display composition‐dependent tailorable optical waveguiding behaviors. While An‐PMDA@Ph‐PMDA core‐shell microrods present wavelength‐dependent two‐photon excited fluorescence performances. The rational creation of these homogeneous and heterogeneous CT‐assembled architectures provides us a deep insight to investigate multicomponent functional organic cocrystals.

Funder

National Natural Science Foundation of China

Tianjin University

Publisher

Wiley

Subject

Electrochemistry,Condensed Matter Physics,Biomaterials,Electronic, Optical and Magnetic Materials

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