Because of their unique structural and optical properties, 1D perylene diimide (PDI) derivatives have gained attention for use in optoelectronic devices. However, PDI‐containing self‐assembled supramolecular systems often are of limited use because they have supramolecular architectures that are held together by weak noncovalent π–π stacking, hydrogen bonding, and hydrophobic interactions. As a result, they are intrinsically unstable under solution‐processing conditions. To overcome this limitation, a polydiacetylene (PDA)‐based strategy is developed to construct a solvent‐resistant and stable PDI assembly. For this purpose, first the monomer PDI–BisDA is generated, in which two polymerizable diacetylene (DA) units are covalently linked to a PDI core. Importantly, 254 nm UV irradiation of self‐assembled PDI–BisDA nanofibers forms solvent‐resistant and stable PDI–PDA fibers. Owing to the presence of PDA, the generated polymer fibers display an increased photocurrent. In addition, the existence of PDA and PDI moieties in the fiber leads to the occurrence of switchable on–off fluorescence resonance energy transfer (FRET) between the PDI and reversibly thermochromic PDA chromophores.
Organic supercapacitors have attracted interest as promising “green” and efficient components in energy storage applications. A polydiacetylene derivative coupled with reduced graphene oxide was employed, for the first time, to generate an organic pseudocapacitance‐based supercapacitor that exhibited excellent electrochemical properties. Specifically, diacetylene monomers were functionalized with perylenediimide (PDI), spontaneously forming elongated microfibers. Following polymerization through UV irradiation, the PDI–polydiacetylene microfibers were interspersed with reduced graphene oxide (rGO), generating a porous electrode material exhibiting a high surface area and facilitating efficient ion diffusion, both essential preconditions for supercapacitor applications. We show that PDI–polydiacetylene has an important role in enhancing the electrochemical properties as a supercapacitor electrode. Besides stabilizing the microporous electrode organization, the delocalized π electrons in both the PDI residues and conjugated network of the polydiacetylene contributed to a significantly higher capacitance (specific capacitance >600 F g−1 at 1 A g−1 current density), longer discharge time, and high power density. The PDI–polydiacetylene‐rGO electrodes were employed in a functional supercapacitor device.
Self-assembly is a dynamic process that often takes place through a stepwise pathway involving formation of kinetically favored metastable intermediates prior to generation of a thermodynamically preferred supramolecular framework. Although trapping intermediates in these pathways can provide significant information about both their nature and the overall self-assembly process, it is a challenging venture without altering temperature, concentrations, chemical compositions and morphologies. Herein, we report a highly efficient and potentially general method for “trapping” metastable intermediates in self-assembly processes that is based on a photopolymerization strategy. By employing a chiral perylene-diimide possessing a diacetylene containing an alkyl chain, we demonstrated that the metastable intermediates, including nanoribbons, nanocoils and nanohelices, can be effectively trapped by using UV promoted polymerization before they form thermodynamic tubular structures. The strategy developed in this study should be applicable to naturally and synthetically abundant alkyl chain containing self-assembling systems.
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