Interactions between lone pairs and aromatic π systems are significant across biology and self-assembled materials. Herein, employing an achiral confinement metal-organic framework (MOF) encapsulates guest molecules, it is successfully realized that lone pair (lp)-π interaction induces fluorescence "turn-on" and circularly polarized luminescence for the first time. The MOFs synthesized based on naphthalenediimide show nearly non-emissive, which can be light-up by introducing acetone or ester guests containing lone pairs-π interaction. Furthermore, the introduction of a series of lp-rich chiral esters induces supramolecular chirality as well as circularly polarized luminescence in achiral MOFs, while also observing chiral adaptability. This work first demonstrates the luminescence and chiral induction via lone pair electrons-π interactions, presenting a fresh paradigm for the advancement of chiroptical materials.
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http://dx.doi.org/10.1002/advs.202406890 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
The magnetic and magneto-optical properties of a tetrazinyl radical-bridged Er metallocene, [(Cp*Er)(bpytz)][BPh] (; Cp* = pentamethylcyclopentadienyl, bpytz = 3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine), are reported. As confirmed by these studies strong Ln-rad coupling is achieved, with exhibiting slow magnetic relaxation under a 1000 Oe dc field. The optical and magneto-optical profile of is completed by both near-infrared (NIR) luminescence and magnetic circularly polarized luminescence (MCPL), representing the first example of NIR MCPL with Er.
View Article and Find Full Text PDFNat Commun
January 2025
Key Laboratory for Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
The preparation of single-crystal polymers with circularly polarized luminesce (CPL) remains a challenging task in chemistry and materials science. Herein, we present the single-crystal-to-single-crystal topochemical photopolymerization of a chiral organic salt to achieve this goal. The in-situ reaction of 1,4-bis((E)-2-(pyridin-4-yl)vinyl)benzene (1) with chiral (+)- or (-)-camphorsulfonic acid (CSA) gives the monomer crystal 1[( + )/( - )-CSA] showing yellow CPL with a high luminescent dissymmetry factor |g| of 0.
View Article and Find Full Text PDFLight Sci Appl
January 2025
Department of Material Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang, Republic of Korea.
Achiral dielectric nanostructures provide an efficient method for discriminating left- and right-circularly polarized photons, leveraging the photothermoelectric effect.
View Article and Find Full Text PDFACS Appl Opt Mater
December 2024
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245, United States.
Angew Chem Int Ed Engl
January 2025
Institute of Chemistry, CAS, Laboratory of Colloid and Interface Scie, Zhong Guancun, 100080, Beijing, CHINA.
Here, we report the synthesis and self-assembly of a novel chiral 2,3:6,7‒naphthalenediimide-based triangular macrocycle (NDI-∆) and their chiroptical properties. The enantiomeric NDI-∆ is synthesized by condensation of (RR) or (SS)-trans-1,2-cyclohexanediamine and 2,3,6,7-naphthalenetetracarboxylic 2,3:6,7-dianhydride, in which the chirality of the macrocycles is controlled by the diamine. With the rigid outer π-surface, the macrocycle showed unique chiroptical properties and self-assembly modes.
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