Manipulating non-innocent π-spacers: the challenges of using 2,6-disubstituted BODIPY cores within donor–acceptor light-harvesting motifs

Bonnier, Catherine; Machin, Devin D.; Abdi, Omar; Koivisto, Bryan D.

doi:10.1039/c3ob40213d

Cited by 53 publications

(69 citation statements)

References 10 publications

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“…D and A represent electron-donor and electron-acceptor groups, respectively (I-III, ref 7c - published by The Royal Society of Chemistry).…”

Section: Figurementioning

confidence: 99%

“…To date, the push-pull effect has been investigated on three BODIPY platforms of types I, II and III (Figure 1) bearing both electron donor (D) and acceptor (A) moieties. 7 In addition, the investigation of push-pull effects on aza-BODIPY platforms has been reported. 8 …”

Section: Introductionmentioning

confidence: 99%

“…9,8b For example, the presence of an electron-donating group (e.g., 4-aminophenyl) and an electron-withdrawing group (e.g., 4-methoxycarbonylphenyl) on the BODIPY platform can greatly enhance the charge transfer within the molecule, for potential applications in dye-sensitized solar cells, 7, 10 and two-photon excitation dyes. 2a, 11 These push-pull effects can also significantly red-shift the absorption and emission spectra of BODIPYs to the near-infrared region, therefore making them attractive for biological imaging and biosensing applications.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Spectroscopic Investigation of a Series of Push–Pull Boron Dipyrromethenes (BODIPYs)

Xuan

Zhao

et al. 2017

J. Org. Chem.

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A series of push-pull BODIPYs bearing multiple electron-donating and electron-acceptor groups were synthesized regioselectively from 2,3,5,6,8-pentachloro-BODIPY, and characterized by NMR spectroscopy, HRMS and X-ray crystallography. The influence of the push-pull substituents on the spectroscopic and electrochemical properties of BODIPYs was investigated. Bathochromic shifts were observed for both absorbance (up to 37 nm) and emission (up to 60 nm) in different solvents upon introduction of the push-pull moieties. DFT calculations, consistent with the spectroscopic and cyclic voltammetry studies, show decreased HOMO-LUMO energy gaps upon the installation of the push-pull moieties. BODIPY 7 bearing thienyl groups on the 2 and 6 positions showed the largest λmax for both absorption (635–653 nm) and emission (706–707 nm), but also the lowest fluorescence quantum yields. All BODIPYs were non-toxic in the dark (IC50 > 200 μM) and showed low phototoxicity (IC50 > 100 μM, 1.5 J/cm2) toward human HEp2 cells. Despite the relatively low fluorescence quantum yields, the push-pull BODIPYS were effective for cell imaging, readily accumulating within cells and localizing mainly in the ER and Golgi. Our structure-property studies can guide future design of functionalized BODIPYs for various applications, including bioimaging and in dye-sensitized solar cells.

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“…D and A represent electron-donor and electron-acceptor groups, respectively (I-III, ref 7c - published by The Royal Society of Chemistry).…”

Section: Figurementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis and Spectroscopic Investigation of a Series of Push–Pull Boron Dipyrromethenes (BODIPYs)

Xuan

Zhao

et al. 2017

J. Org. Chem.

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“…49–51 Functionalized BODIPYs can be conjugated to peptides or proteins for imaging applications using “click” reactions, 44,52–54 traditional amide bond formation reactions, 30,55–58 or solid support methodologies. 59 However, several challenges have hindered their applications using these conjugation methods.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of BODIPY-Peptide Conjugates for Fluorescence Labeling of EGFR Overexpressing Cells

et al. 2017

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Regioselective functionalization of 2,3,5,6,8-pentachloro-BODIPY 1 produced unsymmetric BODIPY 5, bearing an isothiocyanate group suitable for conjugation, in only four steps. The X-ray structure of 5 reveals a nearly planar BODIPY core with aryl dihedral angles in the range 47.4° – 62.9°. Conjugation of 5 to two EGFR-targeting pegylated peptides, 3PEG-LARLLT (6) and 3PEG-GYHWYGYTPQNVI (7), under mild conditions (30 min at room temperature), afforded BODIPY conjugates 8 and 9 in 50–80% isolated yields. These conjugates show red-shifted absorption and emission spectra compared with 5, in the near-IR region, and were evaluated as potential fluorescence imaging agents for EGRF over-expressing cells. SPR and docking investigations suggested that conjugate 8 bearing the LARLLT sequence binds to EGFR more effectively than 9 bearing the GYHWYGYTPQNVI peptide, in part due to the lower solubility of 9, and its tendency for aggregation at concentrations above 10 μM. Studies in human carcinoma HEp2 cells over-expressing EGFR, demonstrated low dark and photo-cytotoxicities for BODIPY 5 and the two peptide conjugates, and remarkably high cellular uptake for both conjugates 8 and 9, up to 90-fold compared with BODIPY 5 after 1 h. Fluorescence imaging studies in HEp2 cells revealed subcellular localization of the BODIPY-peptide conjugates mainly in the Golgi apparatus and the cell lysosomes. The low cytotoxicity of the new conjugates and their remarkably high uptake into EGFR over-expressing cells renders them promising imaging agents for cancers over-expressing EGFR.

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“…This is due to their remarkable properties, including strong absorptions and sharp emissions in the UV/Vis region, relatively high photostability and solubility, and ease of tunability of their physicochemical properties. 1 Over the past three decades, a large number of new BODIPYs were synthesized, characterized and investigated as fluorescent labelling agents for proteins or DNA, 2 as biological imaging probes, 3 in dye-sensitized solar cells (DSSCs), 4 and as photodynamic therapy (PDT) sensitizers. 5 …”

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confidence: 99%

Synthesis and regioselective functionalization of perhalogenated BODIPYs

et al. 2016

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Three perhalogenated BODIPYs (1b–3b), bearing chloro and bromo groups at all carbon positions, were synthesized and characterized. The reactivity of BODIPY 3b was investigated under Stille cross-coupling reactions, and single crystal X-ray analysis was used to confirm the regioselectivity of the reactions. Further substitution at the boron atom produced nona-functionalized BODIPYs 7a,b, which show 676 and 739 nm emissions with 91 and 100 nm Stokes shifts, respectively.

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Manipulating non-innocent π-spacers: the challenges of using 2,6-disubstituted BODIPY cores within donor–acceptor light-harvesting motifs

Cited by 53 publications

References 10 publications

Synthesis and Spectroscopic Investigation of a Series of Push–Pull Boron Dipyrromethenes (BODIPYs)

Synthesis and Spectroscopic Investigation of a Series of Push–Pull Boron Dipyrromethenes (BODIPYs)

Synthesis of BODIPY-Peptide Conjugates for Fluorescence Labeling of EGFR Overexpressing Cells

Synthesis and regioselective functionalization of perhalogenated BODIPYs

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