Flapping Peryleneimide as a Fluorogenic Dye with High Photostability and Strong Visible‐Light Absorption

Kimura, Ryo; Kuramochi, Hikaru; Liu, Pengpeng; Yamakado, Takuya; Osuka, Atsuhiro; Tahara, Tahei; Saito, Shohei

doi:10.1002/anie.202006198

Cited by 44 publications

(35 citation statements)

References 62 publications

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“…This multifold columnar p-stacking is unique for the flapping molecules bearing the central COT ring without bulky substituents. 22,23 Fig. 2.…”

Section: Synthesis and Characterization Of The Flapping Molecular Probementioning

confidence: 99%

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Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of Dual Fluorescent Flapping Dopant

Goto¹,

omagari²,

sato³

et al. 2021

Preprint

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Polymer free volume is a rational concept for interpreting polymer properties connected to the fraction of unoccupied volume. While arbitrary definition of “free volume” often led to controversy, quantitative evaluation of polymer free volume is important for developing membrane materials as well as packing materials for chromatography that adsorb, diffuse, and separate small molecules. Local free volume moves from moment to moment due to thermal fluctuation of surrounding polymer chains. To evaluate the free volume directly and quantitatively, several approaches have been established such as positron annihilation lifetime spectroscopy (PALS), inverse gas chromatography (IGC), 129Xe NMR spectroscopy, and molecular probe. In recent years, some studies have been reported that compare experimental results with molecular dynamics (MD) simulation. However, real-time monitoring of the local free-volume dynamics has only been achieved by single-molecule spectroscopy (SMS) analysis of conformationally flexible probes. In this report, single-molecule fluorescence lifetime has been analyzed because the conformational change of the fluorescent probe, twisted peryleneimide, results in very little spectral difference. This work is an example of the great potential that the SMS technique holds for spatially-resolved dynamic studies of polymers and soft matter in general. Apart from free-volume probing, SMS has been used, e.g., to analyze heterogeneity of local relaxation processes of polymers near glass transition temperature (Tg), to characterize diffusion in solutions or melts, or to monitor polymerization reactions on molecular level. In particular, the SMS method could be an attractive alternative to tracking the dynamics of the polymer free volume because of its high location specificity, suitable dynamic range, non-invasive nature, and relatively affordable and simple optical instrumentation. Here we succeeded in demonstrating such free-volume monitoring by developing a new flexible fluorophore, nitrogen-embedded flapping molecule (N-FLAP), that shows dual fluorescence (FL) spectrum depending on the bent/planar conformations. Compared with the previously reported flapping anthracene, the nitrogen-embedded molecular framework led to much improved FL brightness as well as high photostability, when excited by a visible light. With this unique molecular probe physically doped in polystyrenes, SMS study has been performed to demonstrate that dynamic nanoscale changes of polymer free volume can be monitored in real time by following environment-induced spectral changes of a single N-FLAP molecule. In this way, the probe is capable of visualizing local free volume changes on the order of 200 Å3 on millisecond time scales for extended periods of time. The use of single-molecule imaging techniques can, in principle, provide also 3-dimensional localization of the probe and enable position-dependent studies of the free volume dynamics.

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“…This multifold columnar p-stacking is unique for the flapping molecules bearing the central COT ring without bulky substituents. 22,23 Fig. 2.…”

Section: Synthesis and Characterization Of The Flapping Molecular Probementioning

confidence: 99%

“…N-FLAP was newly prepared by the Pd-catalyzed phenazine synthesis. 22 The coupling reaction of 2,3,8,9-tetrabromodibenzo[a,e]COT 1 23 and 4,5-bis(hexyloxy)benzene-1,2-diamine 2 followed by an in-situ oxidation provided N-FLAP in 45% yield (Fig. 2a).…”

Section: Synthesis and Characterization Of The Flapping Molecular Probementioning

confidence: 99%

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of Dual Fluorescent Flapping Dopant

Goto¹,

omagari²,

sato³

et al. 2021

Preprint

Self Cite

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“…15,16 Overall, flexible conformation will cause the emission wavelength redshift and luminescence efficiency decrease, while rigid conformation will suppress the non-radiative decay and thus alleviate the luminescence efficiency. [17][18][19] Despite lots of strategies have been proposed to prepare luminescent materials with diverse colors and efficiency, [20][21][22][23] it is still challenging to design efficient deep red/near-infrared (DR/NIR) luminogens (650-1300 nm) since non-radiative decay is generally more competitive to radiative decay in this wavelength region due to the intrinsic energy gap law and some fluorescence quenching factors like twisted intramolecular charge transfer (TICT) and strong intermolecular interactions etc. [24][25][26] In this regard, designing luminescent materials by conformation control possibly helps to improve the luminescence efficiency of DR/NIR luminogens because both strong intermolecular interaction and structure rigidity could be tuned by conformation control to facilitate the luminescence efficiency.…”

Section: Introductionmentioning

confidence: 99%

A Bright Deep-Red AIEgen with Locked Noncoplanar Conformation for Lipid Droplet-Specific Imaging

Xing¹,

Park²,

Zhang³

et al. 2020

Preprint

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In the field of fluorescent materials, bright deep-red/near-infrared (DR/NIR) luminogens are always in demand whose rationally and accurately design yet are challenging. Current design strategy of DR/NIR emitters mainly depends on the construction of large p-conjugation and strong donor-acceptor system, which commonly suffers the quenching factors from p-p stacking and twisted intramolecular charge transfer (TICT) effect. In this work, we employed the non-covalent interactions and constructed a luminogen with rigid and twisted conformation, which not only red-shifts the emission wavelength of the luminogen to DR/NIR region but also effectively suppresses the non-radiative decay by p-p stacking and TICT. Moreover, the rational molecular design endows the new luminogen with two-photo absorption capability and superior selectivity towards lipid droplets in different levels including living cells, tissues, and live fish embryo. This work thus presents an elegant, facile and efficient strategy for generating functional DR/NIR emitters.

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“…In addition to FLAP1, the corresponding benzo-peryleneimide Wing1 (Figure 2 e) was synthesized as a reference compound (Scheme S1). Single-crystals of FLAP1 were obtained from toluene/i-PrOH, and the X-ray structure analysis [27] revealed a bent structure with both COT bending angles, [22] defined in Figure 4, of q = 42.58. Bulky substituents inhibited intermolecular p stacking, which resulted in good solubility of FLAP1 in common organic solvents, including simple alkanes.…”

mentioning

confidence: 99%

“…In the X-ray crystal structure of FLAP1 (bottom), para-tert-butylphenoxy groups and hydrogens were omitted for clarity. [27]…”

mentioning

confidence: 99%

Flapping Peryleneimide as a Fluorogenic Dye with High Photostability and Strong Visible‐Light Absorption

et al. 2020

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Flapping fluorophores (FLAP) with a flexible 8π ring are rapidly gaining attention as a versatile photofunctional system. Here we report a highly photostable “flapping peryleneimide” with an unprecedented fluorogenic mechanism based on a bent‐to‐planar conformational change in the S1 excited state. The S1 planarization induces an electronic configurational switch, almost quenching the inherent fluorescence (FL) of the peryleneimide moieties. However, the FL quantum yield is remarkably improved with a prolonged lifetime upon a slight environmental change. This fluorogenic function is realized by sensitive π‐conjugation design, as a more π‐expanded analogue does not show the planarization dynamics. With strong visible‐light absorption, the FL lifetime response synchronized with the flexible flapping motion is useful for the latest optical techniques such as FL lifetime imaging microscopy (FLIM).

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Flapping Peryleneimide as a Fluorogenic Dye with High Photostability and Strong Visible‐Light Absorption

Cited by 44 publications

References 62 publications

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of Dual Fluorescent Flapping Dopant

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of Dual Fluorescent Flapping Dopant

A Bright Deep-Red AIEgen with Locked Noncoplanar Conformation for Lipid Droplet-Specific Imaging

Flapping Peryleneimide as a Fluorogenic Dye with High Photostability and Strong Visible‐Light Absorption

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