BODIPY Moiety Research Articles

One-pot synthesis and properties of well-defined butadiynylene-BODIPY oligomers.

A homogeneous series of well-defined butadiynylene-BODIPY oligomers containing up to four BODIPY moieties have been synthesized from a "one-pot" oxidative homocoupling reaction of 2,6-di((trimethylsilyl)ethynyl)BODIPY. Further derivation of the resultant BODIPY dimer generates a water-soluble, red-emitting butadiyne-linked BODIPY dimer with pyridinium ions, which can ratiometrically detect viscosity, based on the two fluorescent conformers with the two BODIPY cores twisted and planar to each other depending on the viscosity of the environment.

Triplet-triplet annihilation upconversion kinetics of C60-Bodipy dyads as organic triplet photosensitizers.

Three new triplet photosensitizers consisting of a bodipy derivative and C60 moieties were synthesized for triplet-triplet annihilation upconversion of perylene. With the extension of the π-conjugated structure of the bodipy derivative, the three photosensitizers exhibited different absorption wavelengths, e.g. 517 nm for B-2, 532 nm for B-4, and 557 nm for B-6. The steady-state and transient absorption, steady-state fluorescence, and upconverted fluorescence emission were investigated to reveal step-by-step the dynamic processes of the above systems. The quantum yields of intramolecular energy transfer, intersystem crossing, and triplet-triplet energy transfer were measured. From the upconverted fluorescence emission spectra, the overall quantum yield of the triplet-triplet annihilation upconversion, ΦUC, was determined to be 5.80% for B-2, 7.95% for B-4, and 4.99% for B-6.

Synthesis and photophysical properties of a bichromophoric system hosting a disaccharide spacer.

The synthesis of an efficient energy donor-acceptor system is reported, together with its photophysical properties. The bichromophoric species has been conceived to show potentialities for biological applications since a biocompatible disaccharide spacer, constituted of d-galactose and d-glucose derivatives, was used in compound 12 to connect two BODIPY units with different absorption/emission properties. The luminescence spectrum in acetonitrile of 12 shows an intense fluorescence band with a maximum at about 770 nm that is almost identical to that of the lowest-energy BODIPY, regardless of the excitation wavelength used. The quantum yield is 0.2 with an excited state lifetime of 2.5 ns. Excitation and ultrafast transient absorption spectroscopy demonstrates that a very efficient energy transfer takes place in 12 from the highest-energy lying BODIPY subunit to the lowest-energy emissive BODIPY moiety, with a time constant of about 31 ps. Noteworthily, the emission of 12 falls in the near infrared window, suitable for potential biological applications.

BODIPY-17α-ethynylestradiol conjugates: Synthesis, fluorescence properties and receptor binding affinities

In vivo imaging of estrogen receptor (ER) densities in human breast cancer is a potential tool to stage disease, guide treatment protocols and follow-up on treatment outcome. Both positron emission tomography (PET) and fluorescence imaging have received ample attention to detect ligand-ER interaction. In this study we prepared BODIPY-estradiol conjugates using 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) as fluorescent probe and estradiol derivatives as ligand and established their relative binding affinity (RBA) for the ERα. The synthesis of the conjugates involves attachment of a BODIPY moiety to the C17α-position of estradiol using Sonogashira or click reactions of iodo-BODIPY or aza-BODIPY with various 17α-ethynylestradiol (EE2) derivatives. The highest RBA for the ERα was observed with the EE2-BODIPY conjugate (7) featuring a linear eight carbon spacer chain. Cell uptake studies and in vivo imaging experiments in an ER-positive mouse tumor model are in progress.

Photophysical and Electrochemical Characterization of BODIPY-Containing Dyads Comparing the Influence of an A-D-A versus D-A Motif on Excited-State Photophysics.

A complete photophysical characterization of organic molecules designed for use as molecular materials is critical in the design and construction of devices such as organic photovoltaics (OPV). The nature of a molecule's excited state will be altered in molecules employing the same chromophoric units but possessing different molecular architectures. For this reason, we examine the photophysical reactions of two BODIPY-based D-A and A-D-A molecules, where D is the donor and A is the acceptor. A BODIPY (4,4'-difluoro-4-bora-3a,4a-diaza-s-indacene) moiety serves as the A component and is connected through the meso position using a 3-hexylthiophene linker to a N-(2-ethylhexyl)dithieno[3,2-b:2',3'-d]pyrrole (DTP), which serves as the D component. An A-D-A motif is compared to its corresponding D-A dyad counterpart. We show a potential advantage to the A-D-A motif over the D-A motif in creating longer-lived excited states. Transient absorption (TA) spectroscopy is used to characterize the photophysical evolution of each molecule's excited state. Global analysis of TA data using singular value decomposition and target analysis is performed to identify decay-associated difference spectra (DADS). The DADS reveal the spectral features associated with charge-transfer excited states that evolve with different dynamics. A-D-A possess slightly longer excited-state lifetimes, 42 ps nonradiative decay, and 4.64 ns radiative decay compared to those of D-A, 24 ps nonradiative decay, and 3.95 ns radiative decay. A longer lived A-D-A component is observed with microsecond lifetimes, representing a small fraction of the total photophyscial product. Steady-state and time-resolved photoluminescence augment the insights from TA, while electrochemistry and spectroelectrochemistry are employed to identify the nature of the excited state. Density functional theory supports the observed electronic and electrochemical properties of the D-A and A-D-A molecules. These results form a complete picture of the electronic and photophysical properties of D-A and A-D-A and provide contextualization for structure-function relationships between molecules and OPV devices.

A simple fluorescent probe for sensing cysteine over homocysteine and glutathione based on PET

A big challenge is the discrimination of sulfhydryl-containing amino acids due to their structural similarity. We designed and synthesized a simple fluorescent probe 3 for specific detection of cysteine based on photo-induced electron transfer (PET). The acrylate and BODIPY moieties in probe 3 act as a reaction site and reporter group, respectively. So the synergistic effect of the substituent groups endows probe 3 very strong green fluorescence at 525nm (λex=500nm). The cleavage reaction induced by cysteine leads to acrylate hydrolysis, and thereby triggers PET on, which effectively quench the fluorescence of 3. Probe 3 exhibited a rapid response towards cysteine over homocysteine and glutathione. Probe 3 is successfully applied for sensing and imaging cysteine in vitro or in vivo cells with low cytotoxicity.

Synthesis, photoluminescence, chromogenic and fluorogenic discrimination of fluoride and cyanide based on a triphenylamine-tri(2-formyl BODIPY) conjugate

A triphenylamine-decorated BODIPY conjugate (TPA-BODIPY) containing three 2-formyl BODIPY units at one triphenylamine core with electron donor-acceptor structure was synthesized. TPA-BODIPY did not show a twisted intramolecular charge transfer (TICT) effect, possibly because its donor–acceptor effect of was partially blocked by the phenyl bridges. However, its emission can be enhanced by increasing solvent viscosity and decreasing solution temperature, indicating that the aggregation-​induced emission (AIE) effect was caused by the restriction of the intramolecular rotations of luminogens. We also discovered that TPA-BODIPY could be applied as a colorimetric and fluorescent chemosensor for F− and CN− with no interference from each other. The addition of F− and CN− to TPA-BODIPY induced a rapid color change from yellowish green to yellow and flesh, respectively. 19F, 11B and 1H NMR spectra indicated that the preferential binding of cyanide occurred at the boron center of BODIPY core not formyl group. On the other hand, fluoride binding also occurred at the boron center of BODIPY core. However, the BODIPY moiety is presumably decomposed by the cyanide anions in a different way compared to fluoride anions, which can be used as a chemodosimetric probe for F− and CN− ions.

Efficient Photoinduced Charge Separation in a BODIPY–C60 Dyad

A donor–acceptor dyad composed of a BF2-chelated dipyrromethene (BODIPY) and a C60 fullerene has been newly synthesized and characterized. The two moieties are linked by direct addition of an azido substituted BODIPY on the C60, producing an imino–fullerene–BODIPY adduct. The photoinduced charge transfer process in this system was studied by ultrafast transient absorption spectroscopy. Electron transfer toward the fullerene was found to occur selectively exciting both the BODIPY chromophore at 475 nm and the C60 unit at 266 nm on a time scale of a few picoseconds, but the dynamics of charge separation was different in the two cases. Eletrochemical studies provided information on the redox potentials of the involved species and spectroelectrochemical measurements allowed to unambiguously assign the absorption band of the oxidized BODIPY moiety, which helped in the interpretation of the transient absorption spectra. The experimental studies were complemented by a theoretical analysis based on DFT computatio...

Excitation energy deactivation funnel in 3-substituted BODIPY-porphyrin conjugate

BODIPYs absorb in the visible region which is complementary to that of porphyrins and therefore can be suggested as promising antenna groups to improve the light-harvesting potential of porphyrins. A boron-dipyrromethene dye was combined at the 3-position with a Zn-porphyrin to afford a conjugate. The fluorescence of the conjugate was found to originate from the BODIPY moiety independently of the excitation wavelength due to an unique set of energy transfer rates between the BODIPY and Zn-porphyrin moieties. The fluorescence intensity was shown to be tunable over a wide range using the solvent properties. This feature makes the studied BODIPY-porphyrin conjugate a promising compound for the design of new photochromic devices.

Remote Control by π-Conjugation of the Emissive Properties of Fischer Carbene-BODIPY Dyads.

The synthesis, structure, and complete characterization of mono- and bimetallic dyads joining Fischer carbene complexes and BODIPY chromophores are reported. In these organometallic species, the Fischer carbene complex is attached to the BODIPY moiety through a p-aminophenyl group linked at the C8 carbon atom of the BODIPY core. The photophysical properties, namely the corresponding UV/vis absorption and emission spectra of these new metal-carbene complexes, are analyzed and discussed. It is found that whereas the absorption of the considered dyads strongly resembles that of the parent 4-anilinyl-substituted BODIPY, the fluorescence emission is significantly reduced in these species, very likely as a result of a Förster-type energy transfer mechanism. At variance, the replacement of the pentacarbonyl-metal(0) fragment by a carbonyl group leads to high fluorescence emission intensity. In addition, the emissive properties of the BODIPY core in these organometallic dyads can be tuned by remote groups by means of π-conjugation, as supported by density functional theory calculations.

Conjugated Microporous Polymers Incorporating BODIPY Moieties as Light-Emitting Materials and Recyclable Visible-Light Photocatalysts

Here we report the design and synthesis of a new conjugated microporous polymer based on a BODIPY dye (CMPBDP) which has shown excellent luminescence properties and an efficient heterogeneous photocatalytic activity. CMPBDP shows high thermal stability and high surface area with microporous size and efficiently catalyzes the selective oxidation of thioanisole into the corresponding sulfoxide via singlet oxygen under visible light (up to 500 nm). The photocatalytic rate of the heterogeneous materials is 4-fold faster that the corresponding soluble (used as reference) under the same reaction conditions and can be reused several times.

An experimental and theoretical study of dimethylaminostyryl BODIPY-perylenetetracarboxylic derivative dyads: synthesis, properties and DFT calculation

Three novel dyads composed of perylene tetracarboxylic unit and BODIPY moiety were synthesized and subjected to detailed spectroscopic examination and DFT calculations. Comparisons about the physical properties with changed acceptors were made.

Synthesis of a Cationic BODIPY-Containing Conjugated Polymer for Detection of DNA and Cellular Imaging

A water-soluble cationic conjugated polyelectrolyte (P1) containing fluorene, BODIPY and diacetylene moieties was synthesized and characterized. P1 showed two main absorption bands with maxima at 360 and 574nm as well as fluorescence maxima at 648nm due to the incorporation of BODIPY into the polymer backbone. Addition of CT DNA can quench the emission of P1 because of the formation of a P1/CT DNA complex, which was demonstrated by UV-vis spectra and dynamic light scattering (DLS) analyses. Cellular imaging results indicated P1 could be utilized as cellular imaging of HeLa cells, where red fluorescence was observed in the partial cytoplasm. Moreover, CCK-8 assay showed P1 had a low cytotoxicity.

A novel Bodipy-based fluorescent probe for Au3+ ions with high selectivity and its application to bioimaging

A novel fluorescent probe based on a boron dipyrromethene (Bodipy) derivative for Au3+ has been designed, synthesized, and characterized. The probe comprises a spectroscopic unit of Bodipy and a specific Au3+ binding unit of 2-(phenylethynyl)aniline. The probe itself is almost no fluorescence because of photo-induced intramolecular electron transfer from the aniline unit to the Bodipy moiety, whereas transforming the 2-(phenylethynyl)aniline unit into the 2-phenylindole by Au3+ induced intramolecular cyclization reaction gives rise to strong fluorescence emission. In the system, an excellent selectivity toward the detection of Au3+ in aqueous solution over a wide range of tested cations was observed. Moreover, this probe can be used to detect Au3+ in real water samples, and can be used for fluorescent bioimaging of Au3+ in living cells.

BODIPY-Coumarin Conjugate as an Endoplasmic Reticulum Membrane Fluidity Sensor and Its Application to ER Stress Models.

An endoplasmic reticulum (ER) membrane-selective chemosensor composed of BODIPY and coumarin moieties and a long alkyl chain (n-C18) was synthesized. The emission ratio of BODIPY to coumarin depends on the solution viscosity. The probe is localized to the ER membrane and was applied to reveal the reduced ER membrane fluidity under ER stress conditions.

Inside Cover: An Amphiphilic BODIPY‐Porphyrin Conjugate: Intense Two‐Photon Absorption and Rapid Cellular Uptake for Two‐Photon‐Induced Imaging and Photodynamic Therapy (ChemBioChem 16/2015)

The inside cover picture shows an amphiphilic BODPY–porphyrin conjugate BZnPP, a new PDT agent, together with its tumour cell uptake and significant two-photon-induced tumour cell imaging and cytotoxicity. BZnPP consists of a hydrophobic BODIPY moiety and a hydrophilic tetra(ethylene glycol) chain bridging a cationic triphenylphosphonium group linked to an amphiphilic porphyrin matrix ZnP through acetylide linkers at its meso positions. More details can be found in the Full Paper by D. W. J. Kwong, W.-K. Wong, K.-L. Wong, D. Xing et al. on page 2357 in Issue 16, 2015 (DOI: 10.1002/cbic.201500349).

An Amphiphilic BODIPY-Porphyrin Conjugate: Intense Two-Photon Absorption and Rapid Cellular Uptake for Two-Photon-Induced Imaging and Photodynamic Therapy.

The new amphiphilic BODPY-porphyrin conjugate BZnPP and its precursor BZnPH were synthesised, and their linear and two-photon photophysical properties, together with their cellular uptake and photo-cytotoxicity, were studied. This amphiphilic conjugate consists of a hydrophobic BODIPY moiety and a hydrophilic tetra(ethylene glycol) chain bridging a cationic triphenylphosphonium group to an amphiphilic porphyrin ZnP through acetylide linkers at its meso positions. A large two-photon absorption cross-section (σ=1725 GM) and a high singlet oxygen quantum yield (0.52) were recorded. Intense linear- and two-photon-induced red emissions were also observed for both BZnPP and BZnPH. Further in vitro studies showed that BZnPP exhibited very efficient cellular uptake and strong photocytotoxic but weak dark cytotoxic properties towards human breast carcinoma MCF-7 cells. In summary, the two-photon-induced emission and the potent photo-cytotoxicity of BZnPP make it an efficacious dual-purpose tumour-imaging and photodynamic therapeutic agent in the tissue-transparent spectral windows.

Deep-red emissive BODIPY-chlorin arrays excitable with green and red wavelengths.

We report here the synthesis and characterization of BODIPY-chlorin arrays containing a chlorin subunit, with tunable deep-red (641-685 nm) emission, and one or two BODIPY moieties, absorbing at 504 nm. Two types of arrays were examined: one where BODIPY moieties are attached through a phenylacetylene linker at the 13- or 3,13-positions of chlorin, and a second type where BODIPY is attached at the 10-position of chlorin through an amide linker. Each of the examined arrays exhibits an efficient (≥0.80) energy transfer from BODIPY to the chlorin moiety in both toluene and DMF and exhibits intense fluorescence of chlorin upon excitation of BODIPY at ∼500 nm. Therefore, the effective Stokes shift in such arrays is in the range of 140-180 nm. Dyads with BODIPY attached at the 10-position of chlorin exhibit a bright fluorescence in a range of solvents with different polarities (i.e., toluene, MeOH, DMF, and DMSO). In contrast to this, some of the arrays in which BODIPY is attached at the 3- or at both 3,13-positons of chlorin exhibit significant reduction of fluorescence in polar solvents. Overall, dyads where BODIPY is attached at the 10-position of chlorin exhibit ∼5-fold brighter fluorescence than corresponding chlorin monomers, upon excitation at 500 nm.

Improved Spectral Coverage and Fluorescence Quenching in Donor-acceptor Systems Involving Indolo[3-2-b]carbazole and Boron-dipyrromethene or Diketopyrrolopyrrole.

A novel π-conjugated triad and a polymer incorporating indolo[3,2-b]-carbazole (ICZ) and 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) were synthesized via a Sonogashira coupling. Compared to the parent BODIPY the absorption and fluorescence spectrum were for both compounds broader and redshifted. The redshift of the fluorescence and the decrease of the fluorescence quantum yield and decay time upon increasing solvent polarity were attributed to the formation of a partial charge-transfer state. Upon excitation in the ICZ absorption band the ICZ fluorescence was quenched in both compounds mainly due to energy transfer to the BODIPY moiety. In a similar ICZ-π-DPP polymer (where DPP is diketopyrrolopyrrole), a smaller redshift of the absorption and fluorescence spectra compared to the parent DPP was observed. A less efficient quenching of the ICZ fluorescence in the ICZ-π-DPP polymer could be related to the unfavorable orientation of the transition dipoles of ICZ and DPP. The rate constant for energy transfer was for all compounds an order of magnitude smaller than predicted by Förster theory. While in a solid film of the triad a further redshift of the absorption maximum of nearly 100 nm was observed, no such shift was observed for the ICZ-π-BODIPY polymer.

Synthesis and spectral properties of phthalocyanine–BODIPY conjugates

Various zinc phthalocyanines were substituted at ortho or meta positions with 1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (BODIPY) moieties via Pd catalyzed Sonogashira-coupling reactions, at either meso or β positions of the BODIPY. UV–Vis and fluorescence emission spectra of the conjugates exhibit panchromatic behavior due to their absorption over a broad spectral region from ultraviolet to visible and energy transfer from the excited BODIPY substituent to the phthalocyanine core. Some conjugates show red-shifted Q-bands that correlate to the planarity and dihedral angle between the subunits, as well as the position and number of attached BODIPY and phthalocyanine moieties.