An imine linked fluorescent covalent organic cage: the sensing of chloroform vapour and metal ions, and the detection of nitroaromatics

Gajula, Ramesh Kumar; Mohanty, Subhrajit; Chakraborty, Manjari; Sarkar, Moloy; Prakash, M. Durga

doi:10.1039/d1nj00434d

Cited by 10 publications

(8 citation statements)

References 63 publications

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“…Methanol forms strong H‐bonds with the imine functional group of the TBA‐THZ molecule, which might be quenching the emission intensity. The same phenomena we observed in our earlier report with a covalent organic cage molecule [45] . The emission intensity bar graph plot for various solvents is shown in Figure 1(c).…”

Section: Resultssupporting

confidence: 88%

“…The same phenomena we observed in our earlier report with a covalent organic cage molecule. [45] The emission intensity bar graph plot for various solvents is shown in Figure 1(c). The absolute quantum yield data of TBA-THZ and TBA-PH (Table S1) reveal their higher emission properties in medium polar solvents.…”

Section: Uv-vis and Fluorescence Emission Studies Of Tba-thz Moleculementioning

confidence: 99%

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Enhancement of Fluorescence Emission Intensity in a Sulfonyl Hydrazide Derivative of tri(biphenyl‐4‐yl)amine via Solid‐state Grinding with Various Metal Salts: Combined Experimental and Computational Studies

et al. 2023

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Solid‐state fluorescent materials are in huge demand owing to their potential applications in sensors, imaging, and LEDs. The molecular aggregations in the solid state limit their usage in practical applications. Typically, J‐aggregates show enhanced emission, while H‐aggregates show quenching in the solid state. Few supramolecular approaches (like creating hydrogen bonds) were developed to disturb the π–π and other supramolecular interactions in solid‐state H‐aggregates. Herein, we are reporting a p‐toulenesulfonyl hydrazide derivative of tri(biphenyl‐4‐yl)amine (TBA‐THZ) in the solid state showed negligible emission while grinding with M+X− (M+=alkali and alkali earth metal) salts showed enhanced emission. Existing supramolecular interactions were disturbed by dipole‐ion interactions between S=O⋅⋅⋅M+. The micro/nanometer‐sized salt crystal particles serve as templates for the TBA‐THZ molecules, and in the broad sense, the salt crystal surfaces act as a “solid‐state solvent.” The TBA‐THZ ground with various metal salts showed varied emission intensities; the BaCl2 ⋅ 2H2O salt ground sample exhibited the maximum emission intensity. The KPF6+18‐Crown‐6 sample showed 84 times enhanced emission than the pristine TBA‐THZ. The role of 18‐crown‐6 ether was observed as a donor type for K+ ions. The expected S=O⋅⋅⋅K+ dipole‐ion interactions were elucidated through FT‐IR and computational modelling. The slight change in emission wavelength to the higher side after grinding with metal salt indicates that dipole‐ion interactions might slightly modify the chromophore's electronic structure, encouraging radiative decay and higher emission intensity. In contrast, a similar molecule, TBA‐PH, with no sulfonyl functional group, was silent in emission intensity. The TBA‐PH solid has no significant emission even after grinding with metal salts. The emission capacity of the TBA‐THZ salt‐ground powder remained unchanged at higher temperatures and in a highly humid environment. The fluorescent active salt ground matrix of the TBA‐THZ responded admirably to HCl acid fumes and was regenerated upon exposure to ammonia vapours.

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Section: Resultssupporting

confidence: 88%

Section: Uv-vis and Fluorescence Emission Studies Of Tba-thz Moleculementioning

confidence: 99%

Enhancement of Fluorescence Emission Intensity in a Sulfonyl Hydrazide Derivative of tri(biphenyl‐4‐yl)amine via Solid‐state Grinding with Various Metal Salts: Combined Experimental and Computational Studies

et al. 2023

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“…The same phenomenon was observed in our earlier report with fluorescent COC. 11 The photophysical data are presented in Table S3. The fluorescence lifetime data of the COC1 cage in the CHCl 3 solvent were measured by using a time-correlated single photon counting (TCSPC) spectrometer (Life Spec II) along with a 375 nm picosecond diode laser (EPL) as an excitation source.…”

Section: Photophysical Studiesmentioning

confidence: 99%

“…This porosity investigation data is similar to our previous reports of cage molecular crystalline samples. 11,39…”

Section: Nitrogen Gas Adsorption/desorption Studiesmentioning

confidence: 99%

Breaking of J-Aggregates in Fluorescent Covalent Organic Cage Molecular Materials Through Solid State Grinding with Metal Salts: Chemo-Sensing and Light-Emitting Diode Applications

Mahto,

Barik,

Mandal

et al. 2024

ACS Appl. Opt. Mater.

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Covalent organic cages (COCs) show immense potential applications due to their structural flexibility and solution processability. Herein, we report an imine-linked [2 + 3] fluorescent COC (COC1) exhibiting fluorosolvatochromism in the solutions and green luminescence in the solid state. In the crystal, cage molecules form J-aggregates through van der Waals interactions. The C−H•••π interactions within the crystal lattice have been disrupted by grinding the crystals with various inorganic metal salts. This disturbance introduces modifications in the crystalline structure through proposed C−H••• X − (X = oxygen, halogen) interactions. In this context, the metal salt microcrystal surfaces served as a template for the cage molecules and acted as a "solid-state solvent" in a broad sense. Moreover, we have investigated the electroluminescence properties of the cage material, which showed green light emission upon coating the COC1-doped polymer film over the surface of a near-ultraviolet LED, and a thin layer of COC1 along with a red phosphor-doped polymer on the surface of a blue light-emitting diode (LED) resulted in a cool white LED. Furthermore, the cage material exhibited excellent acidochromic properties in the solid and solution states.

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“…The authors have cited additional references within the Supporting Information. [41][42][43][44][45][46][47][48][49][50]…”

Section: Supporting Informationmentioning

confidence: 99%

Emissive Click Cages

Maji,

Samanta,

Samanta

et al. 2023

Chemistry A European J

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Herein, we report the synthesis of cofacial organic cage molecules containing aggregation‐induced emissive (AIE) luminogens (AIEgens) through four‐fold Cu(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) “click” reactions. The shorter AIEgen tetraphenylethylene (TPE) afforded two orientational isomers. The longer building blocks of tetrabiphenylethylene (TBPE) afforded a single isomer. The click reaction employed is irreversible, yet it yields remarkable four‐fold click products above 40%. The phenyl rings around the ethylene core generate propeller‐shaped chirality owing to their orientation, which influences the chirality of the resulting cages. The shorter cages are a mixture of PP/MM isomers, while the longer ones are a mixture of PM/MP isomers, at least in the solid state. The newly synthesized cage molecules were emissive even in dilute solutions (THF) and exhibited enhanced AIE upon the addition of water. Upon aggregation in aqueous solution, the organic cage molecules exhibit turn‐off emission sensing of nitroaromatic explosives with selectivity for picric acid in 25‐38 nanomolar detection range.

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An imine linked fluorescent covalent organic cage: the sensing of chloroform vapour and metal ions, and the detection of nitroaromatics

Abstract: Triphenylamine derived fluorescent covalent organic cage molecule (F-COC) shows enhanced emission doped in polystyrene (PS) when expose to chloroform vapours. Systematic investigation of fluorescence emission intensity of the F-COC in...

Cited by 10 publications

References 63 publications

Enhancement of Fluorescence Emission Intensity in a Sulfonyl Hydrazide Derivative of tri(biphenyl‐4‐yl)amine via Solid‐state Grinding with Various Metal Salts: Combined Experimental and Computational Studies

Enhancement of Fluorescence Emission Intensity in a Sulfonyl Hydrazide Derivative of tri(biphenyl‐4‐yl)amine via Solid‐state Grinding with Various Metal Salts: Combined Experimental and Computational Studies

Breaking of J-Aggregates in Fluorescent Covalent Organic Cage Molecular Materials Through Solid State Grinding with Metal Salts: Chemo-Sensing and Light-Emitting Diode Applications

Emissive Click Cages

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