Unprecedented α-substituted BOPHY dyes via a key 3,8-dichloroBOPHY intermediate

Boodts, Stijn; Hofkens, Johan; Dehaen, Wim

doi:10.1016/j.dyepig.2017.03.046

Cited by 24 publications

(28 citation statements)

References 31 publications

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“…As we have previously reported, [18] the Suzuki and Stille cross‐coupling reactions tend to afford higher yields of functionalized products compared with other coupling reactions, such as Sonogashira and Heck, due to their milder reaction conditions. In addition, as previously reported by Dehaen and coworkers, mono‐substituted BOPHYs are generally less emissive than the corresponding di‐substituted compounds [8] . Therefore, we aimed to synthesize di‐substituted derivatives using an excess amount of the nucleophiles under Suzuki and Stille conditions (Scheme 2).…”

Section: Resultsmentioning

confidence: 94%

“…In addition, as previously reported by Dehaen and coworkers, mono-substituted BOPHYs are generally less emissive than the corresponding di-substituted compounds. [8] Therefore, we aimed to synthesize di-substituted derivatives using an excess amount of the nucleophiles under Suzuki and Stille conditions (Scheme 2). The Suzuki coupling reactions of BOPHY 2 with a variety of arylboronic acids were conducted under the catalysis of Pd(dppf)Cl 2 in the presence of 1 M K 2 CO 3 as the base, in toluene at 80 °C, giving BOPHYs 3-5 in 34 %-85 % yields.…”

Section: Resultsmentioning

confidence: 99%

“…The BOPHY scaffold is composed of a four‐ring structure, with two six‐membered rings in the middle and two pyrroles at the periphery (Figure 1, structure B) [5] . Recently, various functionalization reactions at the BOPHY core, including Knoevenagel condensations, [5a,6] halogenations, [7] palladium(0)‐catalyzed cross‐coupling reactions, [7] and nucleophilic aromatic substitutions, [8] have been investigated. Due to its extended electron delocalization, the BOPHY fluorophore displays a significant bathochromic shift in its absorption and emission spectra compared with BODIPY, and this can be further extended to the near‐IR region via functionalization reactions [9] .…”

Section: Introductionmentioning

confidence: 99%

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Investigations on the Synthesis, Reactivity, and Properties of Perfluoro‐α‐Benzo‐Fused BOPHY Fluorophores

Zhang

Wang

Bobadova‐Parvanova

et al. 2022

Chemistry A European J

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The synthesis and reactivity of 3,8‐dibromo‐dodecafluoro‐benzo‐fused BOPHY 2 are reported, via SNAr with O‐, N‐ S‐ and C‐nucleophiles, and in Pd(0)‐catalyzed cross‐coupling reactions (Suzuki and Stille). The resulting perfluoro‐BOPHY derivatives were investigated for their reactivity in the presence of various nucleophiles. BOPHY 3 displays reversible color change and fluorescence quenching in the presence of bases (Et3N, DBU), whereas BOPHY 7 reacts preferentially at the α‐pyrrolic positions, and BOPHY 8 undergoes regioselective fluorine substitution in the presence of thiols. The structural and electronic features of the fluorinated BOPHYs were studied by TD‐DFT computations. In addition, their spectroscopic and cellular properties were investigated; BOPHY 10 shows the most red‐shifted absorption/emission (λmax 659/699 nm) and 7 the highest fluorescence (Φf=0.95), while all compounds studied showed low cytotoxicity toward human HEp2 cells and were efficiently internalized.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Investigations on the Synthesis, Reactivity, and Properties of Perfluoro‐α‐Benzo‐Fused BOPHY Fluorophores

Zhang

Wang

Bobadova‐Parvanova

et al. 2022

Chemistry A European J

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“…Finally, although 5,5′-dibromoBOPHY 2b has been reported to be unreactive toward metal-catalyzed reactions, we found 2b was successful toward Suzuki and Stille reactions (Scheme ). The usual Suzuki coupling reaction conditions − were used to obtain 4-dimethylaminobenzene-substituted BOPHY 16 in 83% yield. Similarly, the Stille coupling reaction afforded thiophene-substituted BOPHY 17 in 86% yield.…”

Section: Resultsmentioning

confidence: 99%

Polybrominated BOPHY Dyes: Synthesis, Reactivity, and Properties

et al. 2018

J. Org. Chem.

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A series of mono- to hexabrominated BOPHY dyes have been regioselectively synthesized in 41-96% yields from bromination of parent bis(difluoroboron)-1,2-bis((1H-pyrrol-2-yl)methylene)hydrazine (BOPHY), bromination of hydrazine-linked bispyrrole intermediate, or brominated 2-formylpyrrole precursors in moderate to excellent yields. The reactivities of these polybrominated BOPHY dyes were further studied via regioselective nucleophilic substitution or Suzuki/Stille cross-coupling reactions from which a series of 5- or 5,5'-substituted BOPHYs with amine, pyrrole, thiophene, and phenyl groups were obtained in moderate to high yields of 37-94%. The regioselectivities of both the bromination and nucleophilic substitution reaction, and these resultant BOPHY dyes, are confirmed by NMR, HRMS, and crystal structures. The spectroscopic properties of these resultant BOPHYs were studied, and most of them showed strong absorbance and bright fluorescence with maximum wavelengths centered at between the range of 430 and 660 nm. Their absorption and emission spectra were red-shifted for each bromine atom incorporated. The positions in which bromines or substituents are attached modulate the photophysical properties of the resulting BOPHY dyes.

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“…The absorption maximum recorded for PEG‐BOPHY in dilute 2‐methyltetrahydrofuran (MTHF) solution shows a significant red‐shift compared to the parent tetra‐methyl‐BOPHY, (Figure : TM‐BOPHY) as might be expected on the basis of the π‐conjugation length having been extended . The absorption maximum (λ ABS ) lies at 585 nm and the corresponding emission maximum (λ FLU ) is at 615 nm (Figure ).…”

Section: Resultsmentioning

confidence: 90%

Photofading of an Extended BOPHY Chromophore Dispersed in Poly(methyl methacrylate) as a Chemical Actinometer

2018

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The target compound is a member of the symmetric pyrrole-BF 2 family, known as BOPHY, which has been equipped with 3,8styryl groups that push the absorption maximum to lower energy. To assist solubility and facile dispersion in plastic films, poly(ethylene glycol) chains are added to the styryl groups. The photophysical properties are somewhat sensitive to changes in solvent polarity and temperature due to the imposition of weak, intramolecular charge-transfer character. The chromophore bleaches under white-light illumination to form an intermediate species that absorbs and emits at higher energy. This species is believed to be a BOPHY unit with one styryl arm removed from the conjugation path. The intermediate is quite resistant to photobleaching but does fade on prolonged illumination. The kinetics associated with photobleaching in poly(methyl methacrylate) films allow development of a simple model that can be used to establish a robust chemical actinometer for recording exposure to sunlight. Similar photofading behaviour is observed in polar solution, where self-catalysis is observed, with the overall kinetics depending on the nature of the solvent.[a] O.

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Unprecedented α-substituted BOPHY dyes via a key 3,8-dichloroBOPHY intermediate

Cited by 24 publications

References 31 publications

Investigations on the Synthesis, Reactivity, and Properties of Perfluoro‐α‐Benzo‐Fused BOPHY Fluorophores

Investigations on the Synthesis, Reactivity, and Properties of Perfluoro‐α‐Benzo‐Fused BOPHY Fluorophores

Polybrominated BOPHY Dyes: Synthesis, Reactivity, and Properties

Photofading of an Extended BOPHY Chromophore Dispersed in Poly(methyl methacrylate) as a Chemical Actinometer

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