4,4-Difluoro-4-bora-3a,4a-diaza-<i>s</i>-indacene (BODIPY) Dyes Modified for Extended Conjugation and Restricted Bond Rotations

Chen, Jiong; Burghart, Armin; Derecskei‐Kovacs, Agnes; Burgess, Kevin

doi:10.1021/jo991927o

Cited by 267 publications

(142 citation statements)

References 18 publications

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“…Previous works pointed out that the inclusion of bulky groups with free rotation enhances the internal conversion processes, owing to the vibrational coupling, decreasing the fluorescence capacity of the dye. [13] However, in the present case, the bulkiness and disposition of the fluorene moieties, as well as their special proximity, leads to a high sterical hindrance, which should hinder their rotation and hence the non-radiative pathway. Such constrained structures are characterised by improved fluorescence capacities, [ 3d, 14] as is the present case of 1 d (Table 1).…”

Section: Fluorene-bodipy Derivativesmentioning

confidence: 72%

Controlling Optical Properties and Function of BODIPY by Using Asymmetric Substitution Effects

Bañuelos¹,

Agarrabeitia²,

García‐Moreno³

et al. 2010

Chemistry A European J

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Asymmetrically substituted BODIPY analogues of the dye PM567 have been synthesised from 2-acylpyrroles and pyrroles that bear indene, fluorene or difluorene units. The type of linkage between the fluorene and the BODIPY core plays an important role in the photophysics of the BODIPY chromophore. Indeed, an aliphatic bridge gives rise to an energy-transfer process between the chromophores, whereas a vinyl spacer allows an electronic interaction between them, leading to a large red shift of the spectral bands. The laser action of the new dyes has been analysed under transversal pumping at 10 Hz repetition rate, in both liquid phase and incorporated into solid polymeric matrices. Lasing efficiencies of up to 40% were reached with high photostabilities with the laser output remaining at the initial level after 1×10(5) pump pulses in the same position of the sample. The laser action of the new dyes outperforms the laser behaviour of commercial dyes that emit in the same spectral region. The replacement of fluorene by indene quenches the fluorescence and laser emission, but allows the development of an iron cation fluorescent sensor.

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Section: Fluorene-bodipy Derivativesmentioning

confidence: 72%

Controlling Optical Properties and Function of BODIPY by Using Asymmetric Substitution Effects

Bañuelos¹,

Agarrabeitia²,

García‐Moreno³

et al. 2010

Chemistry A European J

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“…Simple, alkyl-substituted dipyrrin BODIPYs, however, display absorption and emission bands with maxima only in the region of 480-540 nm so that today considerable effort is being made to shift the optical properties to the red. [5,[14][15][16][17][18] Several strategies have been reported to be successful such as the introduction of aryl substituents in the 3,5-and/or 1,7-positions of the BODIPY core (like in compounds 4, [19] 5, [20] 6, [21] 7, [22] 8 [23] and 9; [24] Scheme 2) or electron acceptors in the meso position, [25][26][27] aromatic ring fusion, [28][29][30] extension of the electronic p system by styryl substitution [31][32][33][34][35][36][37][38] or aza-substitution of the meso-carbon atom (like in compounds 7 and 9; Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

Dihydronaphthalene‐Fused Boron–Dipyrromethene (BODIPY) Dyes: Insight into the Electronic and Conformational Tuning Modes of BODIPY Fluorophores

Wang

Descalzo

Shen

et al. 2010

Chemistry A European J

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A new series of boron-dipyrromethene (BDP, BODIPY) dyes with dihydronaphthalene units fused to the beta-pyrrole positions (1a-d, 2) has been synthesised and spectroscopically investigated. All the dyes, except pH-responsive 1d in polar solvents, display intense emission between 550-700 nm. Compounds 1a and 1b with a hydrogen atom and a methyl group in the meso position of the BODIPY core show spectroscopic properties that are similar to those of rhodamine 101, thus rendering them potent alternatives to the positively charged rhodamine dyes as stains and labels for less polar environments or for the dyeing of latex beads. Compound 1d, which carries an electron-donating 4-(dimethylamino)phenyl group in the meso position, shows dual fluorescence in solvents more polar than dibutyl ether and can act as a pH-responsive "light-up" probe for acidic pH. Correlation of the pK(a) data of 1d and several other meso-(4-dimethylanilino)-substituted BODIPY derivatives allowed us to draw conclusions on the influence of steric crowding at the meso position on the acidity of the aniline nitrogen atom. Preparation and investigation of 2, which carries a nitrogen instead of a carbon as the meso-bridgehead atom, suggests that the rules of colour tuning of BODIPYs as established so far have to be reassessed; for all the reported couples of meso-C- and meso-N-substituted BODIPYs, the exchange leads to pronounced redshifts of the spectra and reduced fluorescence quantum yields. For 2, when compared with 1a, the opposite is found: negligible spectral shifts and enhanced fluorescence. Additional X-ray crystallographic analysis of 1a and quantum chemical modelling of the title and related compounds employing density functional theory granted further insight into the features of such sterically crowded chromophores.

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“…[4 -6] It has been reported that a modification of the π -conjugation of the molecules results in a redshift of their absorption and emission maxima, [7,8] whereas the introduction of a rigid conformation suppresses the non-radiative decay and resulting in high quantum yields. [9] Thus, structural details of functional dyes play an important role in their structure-function relationship. In this paper, we focus on the structural and conformational characterization of [bis-(N,N -difluoroboryl)]-3,3 -diethyl-4,4 ,8,8 ,9,9 ,10,10 -octamethyl-2,2 -bidipyrrin (1) by NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Conformational dynamics of bis(BF₂)‐2,2′‐bidipyrrins revealed by through‐space ¹³C¹⁹F and ¹⁹F¹⁹F couplings

Xie

Yuan

Krüger

et al. 2009

Magnetic Reson in Chemistry

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The conformation of [bis-(N,N'-difluoroboryl)]-3,3'-diethyl-4,4',8,8',9,9',10,10'-octamethyl-2,2'-bidipyrrin (1) in solution was studied by analyzing the 13C-19F and 19F-19F through-space spin-spin couplings. The 1H and 13C NMR spectra were assigned on the basis of nuclear Overhauser effect spectroscopy (NOESY), heteronuclear single-quantum correlation (HSQC), and heteronuclear multiple-bond correlation (HMBC) experiments. The 19F spectrum of 1 was compared with that of 2-ethyl-1,3,5,6,7-pentamethyl-4,4-difluoro-4-bor-3a,4a-diaza-s-indacen (2). The 19F-19F through-space spin--spin coupling in 1 was thus assigned and the coupling constant was obtained by simulating the coupling patterns. The obtained conformation of 1 was compared with those of the known complexes [bis-(N,N'-difluoroboryl)]-3,3',8,8',9,9'-hexaethyl-4,4',10,10'-tetramethyl-6,6'-(4-methylphenyl)-2,2'-bidipyrrin (3)and [bis-(N,N'-difluoroboryl)]-9,9'-diethyl-4,4',8,8',10,10'-hexamethyl-3,3'-bis(methoxycarbonylethyl)-2,2'-bidipyrrin (4). The conformational dynamics of 1, 3, and 4 was surveyed by observing the temperature dependence of the through-space coupling constants between 253 and 333 K. The 13C-19F and 19F-19F through-space spin-spin couplings thus confirm similar conformations of different BisBODIPYs in solution in contrast to earlier findings in the solid state.

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4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) Dyes Modified for Extended Conjugation and Restricted Bond Rotations

Cited by 267 publications

References 18 publications

Controlling Optical Properties and Function of BODIPY by Using Asymmetric Substitution Effects

Controlling Optical Properties and Function of BODIPY by Using Asymmetric Substitution Effects

Dihydronaphthalene‐Fused Boron–Dipyrromethene (BODIPY) Dyes: Insight into the Electronic and Conformational Tuning Modes of BODIPY Fluorophores

Conformational dynamics of bis(BF₂)‐2,2′‐bidipyrrins revealed by through‐space ¹³C¹⁹F and ¹⁹F¹⁹F couplings

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4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) Dyes Modified for Extended Conjugation and Restricted Bond Rotations

Cited by 267 publications

References 18 publications

Controlling Optical Properties and Function of BODIPY by Using Asymmetric Substitution Effects

Controlling Optical Properties and Function of BODIPY by Using Asymmetric Substitution Effects

Dihydronaphthalene‐Fused Boron–Dipyrromethene (BODIPY) Dyes: Insight into the Electronic and Conformational Tuning Modes of BODIPY Fluorophores

Conformational dynamics of bis(BF2)‐2,2′‐bidipyrrins revealed by through‐space 13C19F and 19F19F couplings

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Conformational dynamics of bis(BF₂)‐2,2′‐bidipyrrins revealed by through‐space ¹³C¹⁹F and ¹⁹F¹⁹F couplings