Mechanochromic luminescence and aggregation induced emission for a metal-free β-diketone

Butler, Tristan; Morris, William A.; Samonina-Kosicka, Jelena; Fraser, Cassandra L.

doi:10.1039/c4cc09439e

Cited by 69 publications

(50 citation statements)

References 60 publications

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“…1,2 Difluoroboron β-diketonate (BF 2 bdk) complexes are of particular interest due to their impressive emission properties and the facile synthesis of β-diketonates via Claisen condensation from a variety of commercially available ketones and esters. 1,3-7 Desirable properties of BF 2 bdks include high extinction coefficients, 8-10 high quantum yields, 8-10 two-photon absorption cross-sections, 8,11 a range of emission colors in solution and the solid state, 10,12 solvatochromism, 4 and the ability to impart significant intramolecular charge transfer (ICT) character in unsymmetrical analogues. 13 Previously we reported the unique mechanochromic luminescent (ML) properties 6,7,12,14,15 of BF 2 bdk dyes as well as their ability to act as dual-emissive ratiometric oxygen sensors in polymer media.…”

Section: Introductionmentioning

confidence: 99%

Stimuli responsive furan and thiophene substituted difluoroboron β-diketonate materials

Morris

Butler

Kołpaczyńska

et al. 2017

Mater. Chem. Front.

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Difluoroboron β-diketonate (BF2bdk) compounds exhibit solid-state switchable luminescence under excitation by UV light. This property is usually manifested as a blue-shift in emission when dye films are thermally annealed followed by a red-shift in response to mechanical shear (i.e. mechanochromic luminescence). Here we report thiophene and furan heterocycle-substituted dyes bearing short methoxy and long dodecyloxy chain substituents. Optical properties of the dyes were investigated in solution, pristine powders, and films on paper and glass. The structural and thermal properties of the dyes were also investigated by powder x-ray diffraction (XRD) and differential scanning calorimetry (DSC), respectively. The methoxy-substituted dyes exhibited neither thermal nor mechano-responsive behavior, however, addition of a longer C12 alkoxyl chain substituent resulted in stimuli-responsive behavior. The furan and thiophene dodecyloxy-substituted dyes both exhibit high-contrast reversible luminescence switching between crystalline, blue-shifted and amorphous red-shifted emissive states. For the furan dye, gentle heating produced a green emissive form while melting followed by rapid cooling produced an orange emissive form. The thiophene dye, on the other hand, exhibited blue-shifted emission when annealed below its melting temperature and red-shifted emission when smeared with a cotton swab (mechanochromic luminescence). These transformations for both dyes were found to be completely reversible, making them potential candidates for applications requiring reusable, functional materials.

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Section: Introductionmentioning

confidence: 99%

Stimuli responsive furan and thiophene substituted difluoroboron β-diketonate materials

Morris

Butler

Kołpaczyńska

et al. 2017

Mater. Chem. Front.

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“…These resultsi ndicated thatt he fluorescencec olor change upon grinding was due to the crystalline-to-amorphous transformation. [37][38][39] The changes in morphologyb etween the original sample (crystalline) and ground sample (amorphous) were also apparent from the SEM images ( Figure S4 in the Supporting Information). After the ground sample was fumigated by EA vapor,t he XRD reflection peaks reappeared along with the recoveryoft he fluorescence.…”

Section: Stimulus-responsive Fluorescent Behaviors Of Solid-state Ndhpmentioning

confidence: 82%

“…These reflection peaks were largely absent from the pattern of the ground sample owing to its amorphous nature. These results indicated that the fluorescence color change upon grinding was due to the crystalline‐to‐amorphous transformation . The changes in morphology between the original sample (crystalline) and ground sample (amorphous) were also apparent from the SEM images (Figure S4 in the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Aggregation‐Induced Emission‐Active 1,4‐Dihydropyridine‐Based Dual‐Phase Fluorescent Sensor with Multiple Functions

Zhou

Chen

Duan

et al. 2019

Chemistry An Asian Journal

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A N‐2‐phenylethyl‐substituted 1,4‐dihydropyridine derivative (NDHP) containing 5,5‐dimethylcyclohexane‐1,3‐dione and naphthylethylene was designed and synthesized. NDHP acts as a multifunctional fluorescent sensor in dual phases. The crystal structure analysis confirms that the NDHP molecules have highly twisted conformations. The twisted conformation results in aggregation‐induced emission properties and solid‐state emission, by restricting the intramolecular free rotation in the aggregated or solid state. In the solid state, NDHP exhibits reversible mechanochromic properties as a result of the transition between the amorphous and crystalline states. NDHP also exhibits a rare phenomenon of acid‐fumed solid‐state emission enhancement owing to the change in packing mode from a zigzag arrangement to J‐aggregation. The solid‐state stimuli‐responsive fluorescence switching is applied to realize a rewritable optical recording media and a multiple output combinational logic system. In solution, NDHP shows a selective fluorescence response for environmentally harmful Hg2+, with a limit of detection of 2.7 nm. This results from the “turn‐on” responsive behavior owing to the Hg2+‐triggered aggregation of the NDHP molecules. NDHP is also used in the imaging of intracellular Hg2+ in HeLa cells. These findings provide a feasible and attractive route for developing multifunctional fluorescent sensors for use in dual phases.

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“…The bdk ligandsw ith different cyclic amine substituents were synthesized using Claisen condensation as previously reported. [27] The BF 2 bdk dyes werep reparedb yb oronation of the ligands using boron trifluoride diethyle therate. [28] For optical property measurements, stock solutions of the bdk ligands and BF 2 bdk dyes were prepared by dissolving compounds in CH 2 Cl 2 .A ppropriate volumeso fs tock solution were then diluted to obtain standard 10 À5 m CH 2 Cl 2 solutions.…”

Section: Synthesis and Optical Propertiesmentioning

confidence: 99%

Ring Size Effects on Multi‐Stimuli Responsive Luminescent Properties of Cyclic Amine Substituted β‐Diketones and Difluoroboron Complexes

Wang

Song

Dickie

et al. 2019

Chemistry An Asian Journal

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Emissive b-diketones (bdks) and difluoroboron complexes (BF 2 bdks) show multi-stimuli responsivel uminescence in both solution and the solid state. As eries of bdk ligands and boron coordinated dyes were synthesized with different cyclic amine substituents in the 4-position to explore ring size effects on variousl uminescent properties, including solvatochromism, viscochromism, aggregation-induced emission (AIE), mechanochromic luminescence( ML) and halochromism. Red-shifted absorption and emission were observed in CH 2 Cl 2 forb oth bdk ligandsa nd boron dyes with increasing substituent ring size. The compounds displayed bathochromic emission in more polar solvents, and higher fluorescence intensity in more viscous media. The AIE compounds exhibited enhanced emission when aggregated. For solid-statep roperties, al arge emission wavelength shift was shown for the piperidine substituted bdk after melt quenching on weighing paper.L arge blue-shifted emissions were observed in all the boron dye spin cast films after trifluoroacetic acid vapor annealing, and the original emissions were partially recovered after triethylamine vapor treatment.

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Mechanochromic luminescence and aggregation induced emission for a metal-free β-diketone

Cited by 69 publications

References 60 publications

Stimuli responsive furan and thiophene substituted difluoroboron β-diketonate materials

Stimuli responsive furan and thiophene substituted difluoroboron β-diketonate materials

Aggregation‐Induced Emission‐Active 1,4‐Dihydropyridine‐Based Dual‐Phase Fluorescent Sensor with Multiple Functions

Ring Size Effects on Multi‐Stimuli Responsive Luminescent Properties of Cyclic Amine Substituted β‐Diketones and Difluoroboron Complexes

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