Circularly-polarized luminescence (CPL) has received new attention on the rise of applications to generate devices and biologically active probes. These applications require fluorophores that are not only chiral but also provide strong fluorescence intensity in aggregated state. Thus, a new research branch has opened up a few years ago, which allows CPL-active fluorophores to be emissive in aggregated-state. As a result, reports on the combination of the CPL property with the aggregation-induced emission (AIE) phenomenon have emerged. Herein the early design principles that have been reported until now to generate CPL-active AIE-active fluorophores (AIEgens) are summarized. In this regard the alignment of monomeric emitters in a chiral fashion, either in supramolecules, polymers or liquid crystals has been proven to be a successful approach. Additionally, first reports have appeared that demonstrate how to tackle the daunting task to furnish individual CPL-active AIEgens.
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http://dx.doi.org/10.1002/smll.201601455 | DOI Listing |
Chem Sci
January 2025
School of Chemistry and Chemical Engineering, Shandong University Jinan 250100 PR China
Noncovalent forces have a significant impact on photophysical properties, and the flexible employment of weak forces facilitates the design of novel luminescent materials with a variety of applications. The arene-perfluoroarene (AP) force, as one type of π-hole/π interaction, shows unique directionality, involving an electron-deficient π-hole interacting with a π-electron-rich region, facilitating precise orientation and stabilization in supramolecular structures. Here we present an amination engineering protocol to build a perfluoroarene library based on an octafluoronaphthalene skeleton with various steric and electronic properties.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
State Key Laboratory of Bio-fibers and Eco-textiles, College of Materials Science and Engineering, Key Laboratory of Shandong Provincial Universities for Advanced Fibers and Composites, Qingdao University, Qingdao, 266071, P. R. China.
A single phenylalanine-based gelator can self-assemble into various chiral nanostructures with triple circularly polarized luminescence (CPL). Its supramolecular assembly and CPL emission are found to be dependent on the kinetic and thermodynamic pathways. This work provides new insight into the regulation of CPL-active functional materials.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, Osaka, 577-8502, Japan.
Circularly polarized luminescence (CPL) and mechanochromic luminescence (MCL) have independently made substantial progress in recent years. However, the exploration of MCL in solid-state CPL materials, which holds practical significance, is still in its infancy. Herein, we report the MCL properties of readily accessible chiral pyrenylprolinamides bearing tert-butoxycarbonyl (Boc) or 2,2,2-trichloroethoxycarbonyl (Troc) groups.
View Article and Find Full Text PDFChemistry
January 2025
Institute of Organic Chemistry PAS: Instytut Chemii Organicznej Polskiej Akademii Nauk, Institute of Organic Chemistry, Kasprzaka 44/52, 01-224, Warsaw, POLAND.
Herein, we report the synthesis and chiroptical characteristics of the first (double) helicenes possesing the 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) moiety as their central core. We have developed a three-step synthesis with 6π-electrocyclization accompanied with HBr elimination as its key step. We found that, whereas for smaller periphereal arms double 6π-electrocyclization occurs smoothly forming a double helicene, in the case of longer policyclic aromatic hydrocarbons the reaction becomes less efficient and mono-helicenes are the only products.
View Article and Find Full Text PDFChem Asian J
January 2025
Universite de Rennes 1, Sciences Chimiques de Rennes - UMR 6226, Avenue du General Leclerc, Campus de Beaulieu, 35042, Rennes, FRANCE.
A novel coordination motif comprising [4]helicene fused with pyrazino-phenanthroline (H4PP) has been synthesized and reacted with ReCl(CO)5 to yield its rhenium(I) complex (Re-H4PP). Absorption and emission spectroscopic analysis conducted in dichloromethane and 2-methyltetrahydrofuran reveals that combining pyrazino-phenanthroline with helicene visibly affects the photophysical attributes of both the resulting ligand and its Re(I) complex as compared to their non-helicene analogues, and even more importantly leads to relatively high photoluminescence quantum yield values, especially in the case of H4PP (29%). Chiroptical studies through electronic circular dichroism and circularly polarized luminescence performed on enantiomerically enriched samples of Re-H4PP show the chiral nature of low-energy excited states affording notable glum values that amplify at cryogenic temperatures.
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