Photolabile coumarins with improved efficiency through azetidinyl substitution

Bassolino, Giovanni; Nançoz, Christoph; Thiel, Zacharias; Bois, Estelle Marine; Vauthey, Eric; Rivera‐Fuentes, Pablo

doi:10.1039/c7sc03627b

Cited by 51 publications

(75 citation statements)

References 33 publications

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“…The fluorescence quantum yield (F f )i saparticularly important factor for fluorescent probes because it often limits practical applications,s uch as environmental monitoring and biosensing events. [21] As observed from the results in Table 2, unlike 4,c hromophores 1-3 preserve lower F f values in CH 2 Cl 2 Figure 2. a) Fluorescence emission spectra of 5 in n-hexane/CH 2 Cl 2 of different ratios at ac oncentration of 10 mm;the excitationwavelengthisl = 400 nm.…”

Section: Resultssupporting

confidence: 59%

Single‐Benzene‐Based Solvatochromic Chromophores: Color‐Tunable and Bright Fluorescence in the Solid and Solution States

Liu

Yan

Huang

et al. 2019

Chemistry A European J

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The search for structurally simple chromophores with superior fluorescence brightness and aw ide range of solventc ompatibility is highly desirable. Herein, an ew type of single-benzene-based solvatochromic chromophore with as ymmetric bifunctional structure, in whicha zetidine and ethoxycarbonyl moietiess erve as the electron-donating and -withdrawing groups, respectively,i sr eported.T his chromophore exhibits an extraordinary wide range of solventc ompatibility and preserves excellent fluorescence quantum yieldsf rom nonpolar n-hexane to polar methanol and even in water.U nusually,t he symmetric structure of the chromophores hows ad istinct color changef rom bright green to red with increasing solvent polaritya nd possesses large Stokess hifts (l = 132-207nm) in the tested solvents. Moreover,t his single-benzene-based chromophored isplays good photochemical stabilityi nb oth solution and solid states, and even exhibits reversible mechanochromic luminescence.[a] Dr.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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Section: Resultssupporting

confidence: 59%

Single‐Benzene‐Based Solvatochromic Chromophores: Color‐Tunable and Bright Fluorescence in the Solid and Solution States

Liu

Yan

Huang

et al. 2019

Chemistry A European J

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“…The four new coumarin derivatives were isolated after silica column chromatography as purple (4Az-6Az) and dark blue (7Az) solids, and their purity was assessed by HPLC ( Figure S3). Characterization was carried out HR ESI-MS and 1D ( 1 H, 13 C, and 19 F) and 2D NMR.…”

Section: Design Synthesis and Characterization Of 7-azetidinyl-coumamentioning

confidence: 99%

“…As previously stated, the stabilization of the TICT excited state is a major cause for fluorescence quenching in polar solvents for many conventional fluorophores, although HBIND has been recently postulated as a deactivation mechanism of the excited state of coumarin 1. 13 Replacement of the 7-N,N-dialkylamino group in conventional coumarins with azetidine lead to a clear improvement in the fluorescent quantum yield of the fluorophore. (e.g.,  F = 0.06 for 1 and  F = 0.92 for 1Az in H 2 O).…”

Section: Photophysical Characterization Of 7-azetidinyl-coupy Fluoropmentioning

confidence: 99%

High Photostability in Nonconventional Coumarins with Far-Red/NIR Emission through Azetidinyl Substitution

et al. 2018

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Replacement of electron-donating N,N-dialkyl groups with three- or four-membered cyclic amines (e.g., aziridine and azetidine, respectively) has been described as a promising approach to improve some of the drawbacks of conventional fluorophores, including low fluorescent quantum yields (Φ) in polar solvents. In this work, we have explored the influence of azetidinyl substitution on nonconventional coumarin-based COUPY dyes. Two azetidine-containing scaffolds were first synthesized in four linear synthetic steps and easily transformed into far-red/NIR-emitting fluorophores through N-alkylation of the pyridine moiety. Azetidine introduction in COUPY dyes resulted in enlarged Stokes' shifts with respect to the N,N-dialkylamino-containing parent dyes, but the Φ were not significantly modified in aqueous media, which is in contrast with previously reported observations in other fluorophores. However, azetidinyl substitution led to an unprecedented improvement in the photostability of COUPY dyes, and high cell permeability was retained since the fluorophores accumulated selectively in mitochondria and nucleoli of HeLa cells. Overall, our results provide valuable insights for the design and optimization of novel fluorophores operating in the far-red/NIR region, since we have demonstrated that three important parameters (Stokes' shifts, Φ, and photostability) cannot be always simultaneously addressed by simply replacing a N,N-dialkylamino group with azetidine, at least in nonconventional coumarin-based fluorophores.

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“…7a). Next, several MOF-based catalysts were explored for this reaction, including VNU-20, Fe 3 O(BDC) 3 2 (DABCO) as catalysts led to higher initial rates. However, 81% and 82% yields were obtained for the reaction aer 6 h. The transformation using the VNU-20 catalyst proceeded with lower initial rate in the rst 4 h reaction time.…”

Section: Catalytic Studiesmentioning

confidence: 99%

“…11 Wang et al synthesized a variety of C-3 functionalized coumarins via the Cu(OAc) 2 catalyzed reaction with cyclic ethers and cycloalkanes. 12 Cao et al developed a novel approach for the direct Csp 2 -H radical triuoromethylation of coumarins in the presence of Mn(OAc) 3 . 13 Zhou et al reported the cross-dehydrogenative coupling of coumarins with benzylic Csp 3 -H bonds utilizing Cu(OAc) 2 catalyst.…”

Section: Introductionmentioning

confidence: 99%

Cross-dehydrogenative coupling of coumarins with Csp³–H bonds using an iron–organic framework as a productive heterogeneous catalyst

Doan

Nguyen

et al. 2018

RSC Adv.

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The iron-organic framework VNU-20 was utilized as an active heterogeneous catalyst for the crossdehydrogenative coupling of coumarins with Csp 3 -H bonds in alkylbenzenes, cyclohexanes, ethers, and formamides. The combination of DTBP as the oxidant and DABCO as the additive led to high yields of coumarin derivatives. The VNU-20 was more active towards this reaction than numerous other homogeneous and heterogeneous catalysts. Heterogeneous catalysis was confirmed for the crossdehydrogenative coupling transformation utilizing the VNU-20 catalyst, and the contribution of active iron species in the liquid phase was insignificant. The iron-based framework was reutilized many times for the functionalization of coumarins without a remarkable decline in catalytic efficiency. To the best of our knowledge, these reactions of coumarins have not previously been conducted using heterogeneous catalysts.

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Photolabile coumarins with improved efficiency through azetidinyl substitution

Abstract: The efficiency of photoactivatable coumarins in water has been enhanced by substitution with azetidine.

Cited by 51 publications

References 33 publications

Single‐Benzene‐Based Solvatochromic Chromophores: Color‐Tunable and Bright Fluorescence in the Solid and Solution States

Single‐Benzene‐Based Solvatochromic Chromophores: Color‐Tunable and Bright Fluorescence in the Solid and Solution States

High Photostability in Nonconventional Coumarins with Far-Red/NIR Emission through Azetidinyl Substitution

Cross-dehydrogenative coupling of coumarins with Csp³–H bonds using an iron–organic framework as a productive heterogeneous catalyst

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Photolabile coumarins with improved efficiency through azetidinyl substitution

Abstract: The efficiency of photoactivatable coumarins in water has been enhanced by substitution with azetidine.

Cited by 51 publications

References 33 publications

Single‐Benzene‐Based Solvatochromic Chromophores: Color‐Tunable and Bright Fluorescence in the Solid and Solution States

Single‐Benzene‐Based Solvatochromic Chromophores: Color‐Tunable and Bright Fluorescence in the Solid and Solution States

High Photostability in Nonconventional Coumarins with Far-Red/NIR Emission through Azetidinyl Substitution

Cross-dehydrogenative coupling of coumarins with Csp3–H bonds using an iron–organic framework as a productive heterogeneous catalyst

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Cross-dehydrogenative coupling of coumarins with Csp³–H bonds using an iron–organic framework as a productive heterogeneous catalyst