Spectral Dispersion and Water Solubilization of BODIPY Dyes via Palladium-Catalyzed C−H Functionalization

Thivierge, Cliferson; Bandichhor, Rakeshwar; Burgess, Kevin

doi:10.1021/ol0706197

Cited by 108 publications

(64 citation statements)

References 21 publications

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“… aryl substitution at the 3 and/or 5 position (e.g., 2 and 5 ) 7–9 ; ethynylphenyl substitution (e.g., 3 ) 10 ; styryl substitution (e.g., 4 ) 11–16 ; vinyl substitution at the 2 and 6 positions 17 ; aryl substitution at the 1, 3, 5, and 7 positions 18 ; exchange of the meso‐ (8)‐carbon for a nitrogen atom (aza‐BODIPYs) together with 1,3,5,7‐tetraaryl substitution (e.g., 6 ) 19–23 ; aromatic ring fusion (e.g., 7 ) 24,25 ; or combinations thereof. …”

Section: Chemical Modification Strategies Toward Long‐wavelength Bodimentioning

confidence: 99%

Red/Near‐infrared Boron–Dipyrromethene Dyes as Strongly Emitting Fluorophores

Descalzo

Shen

et al. 2008

Annals of the New York Academy of Sciences

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We present an overview of the state of the art in long-wavelength boron-dipyrromethene (BODIPY) fluorophores, focusing on strategies to shift the absorption and emission bands into the red/near-infrared (NIR) range of the spectrum. This report also discusses chemical modifications of the chromophoric core to obtain analyte-responsive fluorophores, including examples of pH and metal ion indicators. Finally, we present a new series of phenanthrene-fused BODIPY dyes, emitting with high efficiency in the red/NIR region of the spectrum, as well as discussing potential applications thereof as probes.

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Section: Chemical Modification Strategies Toward Long‐wavelength Bodimentioning

confidence: 99%

Red/Near‐infrared Boron–Dipyrromethene Dyes as Strongly Emitting Fluorophores

Descalzo

Shen

et al. 2008

Annals of the New York Academy of Sciences

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“…A large number of functional groups can be introduced through well-documented synthetic approaches to the BODIPY core, allowing the preparation of sophisticated dyes with fine-tuned optical, ( photo)physical and chemical properties. In recent years, several reactive BODIPY scaffolds have been reported, which allow a nearly unlimited molecular structural modification, e.g., the use of halogenated BODIPYs,8,9 the Liebeskind-Srogl reaction 10 and direct functionalization (e.g., nucleophilic substitution of hydrogen at the 3,5-positions, 11 direct alkenylation 12 and direct borylation 13 at the 2,6-positions). The parent BODIPY dye shows absorption and emission around 500 nm.…”

Section: Introductionmentioning

confidence: 99%

UV—vis spectroscopy of the coupling products of the palladium-catalyzed C—H arylation of the BODIPY core

Wang

Verbelen

Tonnelé

et al. 2013

Photochem Photobiol Sci

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The steady-state, UV-vis electronic absorption and fluorescence emission properties of a large set of 3-aryl and 3,5-diaryl substituted difluoroboron dipyrromethene dyes obtained via direct, palladiumcatalyzed C-H (het)arylation of the BODIPY core are reported. The spectra display the narrow absorption and fluorescence emission bands and the generally quite small Stokes shifts characteristic of classic difluoroboron dipyrrins. As a function of the solvent, the spectral maxima are located within a very narrow wavelength range and are slightly red-shifted with increasing solvent polarizability, which is shown to be the crucial parameter influencing the wavelength position of the maxima. The extended π-conjugation in the 3,5-diaryl products always leads to bathochromically shifted absorption and emission spectra compared to those of the 3-aryl analogues. The derivative with a 3-mesityl substituent has blue-shifted spectra in comparison to its 3-phenyl substituted analogue, reflecting the diminished π-conjugation in the former due to steric strain. The nature of the meso-aryl has only a small effect on the spectral positions but affects the fluorescence quantum yield Φ. The majority of the dyes have high Φ (>0.85), except the compounds with meso-phenyl and meso-( p-nitrophenyl) substituents. Quantumchemical calculations were performed to evaluate the differences in spectroscopic properties upon substitution of the BODIPY core and to compare them with the corresponding experimental results.

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“…Burgess' group has shown that addition of a sulfonate group to the 2- and 6-positions increases aqueous solubility without sacrificing quantum yield 4. They have also made water soluble BDPs for covalent modification of biomolecules and cassettes for energy transfer by appending sulfonic acids to the BDP core and adding carboxylic acid-containing tethers 12, 13. Niu et al have taken a different approach.…”

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confidence: 99%

Synthesis, spectroscopic properties and protein labeling of water soluble 3,5-disubstituted boron dipyrromethenes

Dilek

Bane

2009

Bioorganic & Medicinal Chemistry Letters

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Sulfur-containing 3,5-disubstituted boron dipyrromethene (Bodipy®) fluorescent probes with improved water solubility were synthesized. A dicarboxylic acid derivative that can be excited by the 543 nm HeNe laser line is very soluble in aqueous solution and retains high fluorescence quantum yield of the unionizable parent molecule. Conversion of the dicarboxylic acid to the succimidyl or sulfosuccinimidyl diester produces molecules capable of labeling proteins with a bright and stable fluorescence signal.Boron dipyrromethene fluorophores (Bodipy ® or BDP) are widely used as probes in biological systems. 1 These molecules normally have good photostability and high quantum yields, 2, 3 but they tend to have low aqueous solubility. 4 The absorption and emission maxima can be tuned to chosen regions of the visible to the near-IR region of the electromagnetic spectrum by varying the substituents on the dipyrromethene chromophore. 5-9 Lowering the energy of the absorption maximum often involves addition on unsaturated or aromatic systems, 10, 11 which decreases their aqueous solubility, thereby limiting their utility as biological probes.Recently efforts have been made to increase the aqueous solubility of BDPs. Burgess' group has shown that addition of a sulfonate group to the 2-and 6-positions increases aqueous solubility without sacrificing quantum yield. 4 They have also made water soluble BDPs for covalent modification of biomolecules and cassettes for energy transfer by appending sulfonic acids to the BDP core and adding carboxylic acid-containing tethers. 12, 13 Niu et al. have taken a different approach. They attached hydrophilic molecules containing multiple ionizable groups to various positions on the parent molecule. 14,15 In some cases aqueous concentrations of 100 -750 μM could be obtained.The objective of this work was to make BDP derivatives that fluoresce at long wavelength, are soluble in aqueous solution and can be used for protein labeling. The molecules are based on the 3,5-disubstituted BDP's of Rohand et al., 9 which are easy to synthesize and whose absorption and emission maxima can be tuned by altering the nature of the functional group. 16,17 The sulfur-substituted compounds possessed the best properties for this type of label: absorption maximum near the HeNe 543 nm line and good quantum yield in both polar and apolar environments. 13,18 Reported here is the synthesis and characterization of water soluble BDPs suitable for biological applications. Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Syntheses of the 3,5-substituted BDPs are presented ...

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Spectral Dispersion and Water Solubilization of BODIPY Dyes via Palladium-Catalyzed C−H Functionalization

Abstract: Fluorescent probes 1 and 2 were prepared directly from tetramethyl-BODIPY via palladium-mediated C-H functionalization reactions.

Cited by 108 publications

References 21 publications

Red/Near‐infrared Boron–Dipyrromethene Dyes as Strongly Emitting Fluorophores

Red/Near‐infrared Boron–Dipyrromethene Dyes as Strongly Emitting Fluorophores

UV—vis spectroscopy of the coupling products of the palladium-catalyzed C—H arylation of the BODIPY core

Synthesis, spectroscopic properties and protein labeling of water soluble 3,5-disubstituted boron dipyrromethenes

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