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Tailoring the properties of solid-state organic luminescent materials using a bottom-up design principle is highly desirable for many applications. Herein, we present a "macrocycle-to-framework" strategy to construct macrocycle-functionalized and hydrazone-linked functional organic polymers with bright yellowish-green luminescence and unique solvatochromism behaviors by the condensation of a diacylhydrazine-functionalized pillar[5]arene with tris(4-formylbiphenyl)amine. Outperforming their non-macrocycle-incorporated counterparts, the pillar[5]arene-containing materials display amplified sensitivity to acidic conditions with luminescent and colorimetric dual-modal patterns assisted by the enhanced intramolecular charge transfer (ICT), and exhibit satisfactory responsiveness to nitrobenzene compounds through rapid luminescence quenching with high selectivity and a low detection limit, where the sensing process proceeds through multiple dynamic quenching pathways.
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http://dx.doi.org/10.1002/anie.202206144 | DOI Listing |
Org Lett
September 2025
School of Pharmaceutical and Chemical Engineering and Institute for Advanced Studies, Taizhou University, 1139 Shifu Road, Taizhou, Zhejiang 318000, China.
Here, intramolecular hydrogen bond (IMHBs)-induced rigidity is used for the first time to synthesize macrocyclic arenes. Calix[]azanediyldibenzoates (C[]A, where = 3, 4, or 5) are synthesized through a one-step condensation reaction between dimethyl 2,2'-azanediyldibenzoate and paraformaldehyde. Compared to the monomer, the macrocycles exhibit a fast and significant acidochromic response due to the intramolecular charge transfer that is boosted by the synergistic effect of their adsorption and protonation.
View Article and Find Full Text PDFChem Asian J
August 2025
Functional Organic Molecules Synthesis Laboratory, Department of Chemistry, University of Delhi, Delhi, 110007, India.
In this work, we designed and synthesized D-A type tripodal phenothiazine derivatives to examine the influence of different functional groups on the photophysical properties and response to external stimuli. The compounds show emission in both solution and solid-state. Intramolecular charge transfer (ICT) characteristics are evidenced by the fluorescence studies revealing positive solvatochromism in compounds.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2025
Shanghai Key Laboratory of Advanced Polymeric Materials, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China.
Endowing dual-responsive ultrathin polymersomes (UTPSs) with reversible stimuli-chromic and fluorochromic performances offers a prospective yet challenging strategy for achieving high-level information encryption and anticounterfeiting. Herein, starting from rational synthesis of visible light/pH-responsive integrated azobenzene monomer, side-chain-type amphiphilic alternating azocopolymers were elaborately crafted using a moderate epoxy-amino click-polycondensation. Followed by subsequent solution self-assembly, dual-responsive UTPSs with a diameter of ∼253 nm and a vesicular thickness of ∼2.
View Article and Find Full Text PDFChem Asian J
July 2025
Ural Federal University, 19 Mira Str., Yekaterinburg, 620002, (Russia).
Using the "1,2,4-triazine" methodology, we have designed a series of new 9H-pyrido[2,3-b]indole-based fluorophores/probes 4a-e, 7a,b, and 8a,b. Photophysical studies of the push-pull fluorophores 8a and 8b revealed a positive solvatochromic effect with Δμ > 15D and Stokes shifts of up to 270 nm. Experimental data and theoretical calculations of the ground and excited states of the compounds demonstrated that pyridoindoles 4a-e and 7a,b exhibit a planarized intramolecular charge-transfer (PLICT) state, which is accompanied by a gradual increase in luminescence quantum yield for samples 4d and 7b with increasing solvent polarity.
View Article and Find Full Text PDFChemistry
May 2025
Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Kaiserstraße 12, Karlsruhe, Germany.
5,8-Dihydroindolo[2,3-c]carbazole (ICz), 9H-cinnolino[3,4-c]carbazole (CnCz), and variously alkyl-, alkenyl-, and aryl-substituted indolo[2,3-k]- and -[3,2-a]phenanthridines (IPs) were synthesized using an ortho fusion strategy with Suzuki cross couplings, intramolecular nitrene insertions, diazo couplings, and Morgan-Walls cyclizations as key reactions. The IPs were additionally transformed into organoboranes and helicene conjugates with tetraphenylethylene derivatives. The compounds fluoresce with large Stokes shifts, exhibit strong acidochromism, and show a good to excellent aggregation-induced emission.
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