Synthesis and characterisation of the unsubstituted dipyrrin and 4,4-dichloro-4-bora-3a,4a-diaza-s-indacene: improved synthesis and functionalisation of the simplest BODIPY framework

Groves, Brandon R.; Crawford, Sarah M.; Lundrigan, Travis; Matta, Chérif F.; Sowlati‐Hashjin, Shahin; Thompson, Alison

doi:10.1039/c2cc37480c

Cited by 37 publications

(38 citation statements)

References 20 publications

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“…In these two statuses, λ abs (max) is more red-shifted in the more polarizable solvents toluene and chlorobenzene. Conversely, the values of λ abs (max) of 8-Ph are blue-shifted concerning those of 2-Ph and 3-Ph and are close to those of unsubstituted BODIPY [50,51], ranging from 489 nm in acetonitrile to 497 nm in toluene and chlorobenzene. This absorption energy range is in good agreement with that of other BODIPYs substituted at the meso-position with a weak electron acceptor or donor [52,53].…”

Section: Photophysical Properties Of Bodipy Dyesmentioning

confidence: 72%

Photophysics of BODIPY Dyes: Recent Advances

Çetindere¹

2021

Photophysics, Photochemical and Substitution Reactions - Recent Advances

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BODIPY dyes are unique fluorophores that can be used in numerous application areas because of their interesting photophysical properties such as high molar absorptivity, tunable absorption and emission energies, and high fluorescence quantum yields. They show impressive photophysical property changes upon substitution of functional groups on the main core structure. Exchange of the meso-carbon on dipyrrin core with nitrogen produces an analog class of BODIPY called aza-BODIPY. Up to now, various kinds of BODIPY and aza-BODIPY derivatives have been developed and applied in science and industry. In this chapter, recent studies on photophysical properties of BODIPY derivatives are summarized.

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Section: Photophysical Properties Of Bodipy Dyesmentioning

confidence: 72%

Photophysics of BODIPY Dyes: Recent Advances

Çetindere¹

2021

Photophysics, Photochemical and Substitution Reactions - Recent Advances

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“…In both cases, abs(max) is more red-shifted in the more polarizable solvents toluene and chlorobenzene. In contrast, the values of abs(max) of 8-Ph (with a phenyl substituent at the meso-position) are blue-shifted in relation to those of 2-Ph and 3-Ph and are close to those of unsubstituted boron dipyrromethene, 3,[22][23][24] ranging from 489 nm in acetonitrile to 497 nm in toluene and chlorobenzene: the solvent dependence correlating with the refractive index. This absorption energy range is in good agreement with that of other BODIPYs substituted at the mesoposition with a weak electron acceptor or donor.…”

Section: Spectroscopic and Photophysical Propertiesmentioning

confidence: 81%

“…19 Boron dipyrromethenes, modified at the meso-position with strong electron withdrawing groups, possess large red shifts, [20][21] because the LUMO is highly stabilized 3 compared to unsubstituted BODIPY. 3,[22][23][24] In contrast, electron donating groups at the meso-position cause a blue-shift in the absorption and emission spectra, while keeping high fluorescence quantum yields and lifetimes. [25][26][27][28] Certain modifications at the meso-position may result in almost nonfluorescent compounds, as for meso-alkenyl- 29 or meso-formylBODIPYs.…”

Section: Introductionmentioning

confidence: 99%

Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group

et al. 2016

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Noël (2016) Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group. RSC Advances, 6 . pp. 102899-102913. ISSN 2046-2069 Access from the University of Nottingham repository: http://eprints.nottingham.ac.uk/37842/1/Ph%20Ethyn%20Styryl%20BODIPYs%20-%20Accepted%20Manuscript.pdf Copyright and reuse:The Nottingham ePrints service makes this work by researchers of the University of Nottingham available open access under the following conditions. This article is made available under the University of Nottingham End User licence and may be reused according to the conditions of the licence. For more details see: http://eprints.nottingham.ac.uk/end_user_agreement.pdf A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription.For more information, please contact eprints@nottingham. ABSTRACT. A very active branch of organic chemistry is putting great effort in tailoring fluorescent dyes for a myriad of applications, from technological to bioanalytical and biomedical applications. Among the major families of fluorophores, those derived from 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY dyes) are undergoing a recent boost thanks to the simplicity and robustness of the chemistry involved. The BODIPY core can be modified with numerous side groups, the 8-position being a modification place with important effects on the spectroscopic and photophysical properties of the resulting dyes. Likewise, previous work has shown that the addition of groups attached at the 3-and 2-positions can result in dyes with very different properties. Herein, we generalize the effect of the substituent side groups by studying nine BODIPY dyes substituted with a phenyl, styryl or phenylethynyl moiety at the 2-, 3-or 8-position of the BODIPY scaffold. Within the class of phenyl-or phenylethynyl-substituted dyes, substitution at the 2-position always leads to dyes with the broadest bandwidths and the largest Stokes shifts. We investigate the solvent effect on the spectroscopic properties of the dyes, using four empirical solvent scales (dipolarity, polarizability, acidity and basicity: Catalán, J. Phys. Chem., 2009, 113, 5951). These analyses identify solvent dipolarity and polarizability as critical parameters accounting for the observed solvent-dependent shifts of the absorption and emission maxima. Finally, time-dependent density functional theory calculations provide insights into the structural and energetic issues concerning the spectroscopic properties of these fluorophores.KEYWORDS: Fluorescent dyes, solvent effect, Catalán solvent scales, quantum chemical calculations TOCUnderstanding the spectroscopic properties of BODIPY dyes for a rationale design of tailored fluorescent ...

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“…70% (Scheme 4). 70 At room temperature, the one-pot oxidation of dipyrromethane 29 with DDQ in the presence of pyrrole 18 in chloroform, followed by neutralization with triethylamine and complexation with BF3 . OEt2 provided the desired unsubstituted BODIPY 9 in low yield (10%).…”

Section: Synthesis Of the Parent Unsubstituted Bodipymentioning

confidence: 99%

Synthesis of BODIPY dyes through postfunctionalization of the boron dipyrromethene core

Boens

Verbelen

Ortiz

et al. 2019

Coordination Chemistry Reviews

296

173

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Synthesis and characterisation of the unsubstituted dipyrrin and 4,4-dichloro-4-bora-3a,4a-diaza-s-indacene: improved synthesis and functionalisation of the simplest BODIPY framework

Abstract: An improved and scalable synthesis of the unsubstituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene framework facilitates access to the previously unreported parent dipyrrin HCl salt, as well as 4,4-dichloro-4-bora-3a,4a-diaza-s-indacene.

Cited by 37 publications

References 20 publications

Photophysics of BODIPY Dyes: Recent Advances

Photophysics of BODIPY Dyes: Recent Advances

Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group

Synthesis of BODIPY dyes through postfunctionalization of the boron dipyrromethene core

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