- Bright solid-state red-emissive BODIPYs: facile synthesis and their high-contrast mechanochromic properties
-
Organic compounds with bright solid-state emission are emerging as versatile materials in many fields. However, traditional fluorescent dyes generally show high-emissive fluorescence in solution but faint or quenched emission in the solid state. Therefore, it remains a great challenge to develop bright solid-state emissive materials based on traditional fluorescent dyes. Herein, we report several solid-state emissive meso-substituted BODIPYs (PhMe3-BODIPY, PhMe-BODIPY, Ph-BODIPY and Me-BODIPY) obtained by using a simple two-step synthesis. Interestingly, these BODIPYs exhibit bright dual-state emission (DSE) with green fluorescence (512-520 nm, fluorescence quantum yield ΦF is up to 85%) in THF and solid-state red emission (601-632 nm, ΦF is up to 32.2%) in the crystalline state. The highly emissive fluorescence in the crystalline state is demonstrated to be due to the formation of J-aggregation. More importantly, the single crystals of the meso-aryl-substituted BODIPYs exhibit an unusual high-contrast mechanochromic property, which displays remarkable fluorescence color changes from red to yellow upon gentle grinding due to the transition from single crystals to microcrystals. Furthermore, strong grinding completely destroys the J-aggregation and leads to the transformation from microcrystals to a free state, hence the fluorescence color becomes green after strong grinding.
- Duan, Chong,Zhou, Yibin,Shan, Guo-Gang,Chen, Yuncong,Zhao, Weijun,Yuan, Dandan,Zeng, Lintao,Huang, Xiaobo,Niu, Guangle
-
-
Read Online
- Exploring the Relationship between BODIPY Structure and Spectroscopic Properties to Design Fluorophores for Bioimaging
-
Designing chromophores for biological applications requires a fundamental understanding of how the chemical structure of a chromophore influences its photophysical properties. We here describe the synthesis of a library of BODIPY dyes, exploring diversity at various positions around the BODIPY core. The results show that the nature and position of substituents have a dramatic effect on the spectroscopic properties. Substituting in a heavy atom or adjusting the size and orientation of a conjugated system provides a means of altering the spectroscopic profiles with high precision. The insight from the structure–activity relationship was applied to devise a new BODIPY dye with rationally designed photochemical properties including absorption towards the near-infrared region. The dye also exhibited switch-on fluorescence to enable visualisation of cells with high signal-to-noise ratio without washing-out of unbound dye. The BODIPY-based probe is non-cytotoxic and compatible with staining procedures including cell fixation and immunofluorescence microscopy.
- Donnelly, Joanna L.,Offenbartl-Stiegert, Daniel,Marín-Beloqui, José M.,Rizzello, Loris,Battaglia, Guiseppe,Clarke, Tracey M.,Howorka, Stefan,Wilden, Jonathan D.
-
-
Read Online
- Exploring the Application of the Negishi Reaction of HaloBODIPYs: Generality, Regioselectivity, and Synthetic Utility in the Development of BODIPY Laser Dyes
-
The generality of the palladium-catalyzed C-C coupling Negishi reaction when applied to haloBODIPYs is demonstrated on the basis of selected starting BODIPYs, including polyhalogenated and/or asymmetrical systems, and organozinc reagents. This reaction is an interesting synthetic tool in BODIPY chemistry, mainly because it allows a valuable regioselective postfunctionalization of BODIPY chromophores with different functional groups. In this way, functional patterns that are difficult to obtain by other procedures (e.g., asymmetrically functionalized BODIPYs involving halogenated positions) can now be made. The regioselectivity is achieved by controlling the reaction conditions and is based on almost-general reactivity preferences, and the nature of the involved halogens and their positions. This ability is exemplified by the preparation of a series of new BODIPY dyes with unprecedented substitution patterns allowing noticeable lasing properties.
- Palao, Eduardo,Duran-Sampedro, Gonzalo,De La Moya, Santiago,Madrid, Miriam,García-López, Carmen,Agarrabeitia, Antonia R.,Verbelen, Bram,Dehaen, Wim,Boens, N?el,Ortiz, María J.
-
-
Read Online
- Excitation Energy Delocalization and Transfer to Guests within MII4L6 Cage Frameworks
-
We have prepared a series of MII4L6 tetrahedral cages containing one or the other of two distinct BODIPY moieties, as well as mixed cages that contain both BODIPY chromophores. The photophysical properties of these cages and their fullerene-encapsulated adducts were studied in depth. Upon cage formation, the charge-transfer character exhibited by the bis(aminophenyl)-BODIPY subcomponents disappeared. Strong excitonic interactions were instead observed between at least two BODIPY chromophores along the edges of the cages, arising from the electronic delocalization through the metal centers. This excited-state delocalization contrasts with previously reported cages. All cages exhibited the same progression from an initial bright singlet state (species I) to a delocalized dark state (species II), driven by interactions between the transition dipoles of the ligands, and subsequently into geometrically relaxed species III. In the case of cages loaded with C60 or C70 fullerenes, ultrafast host-to-guest electron transfer was observed to compete with the excitonic interactions, short-circuiting the I → II → III sequence.
- Musser, Andrew J.,Neelakandan, Prakash P.,Richter, Johannes M.,Mori, Hirotaka,Friend, Richard H.,Nitschke, Jonathan R.
-
-
Read Online
- Synthesis of [18F]BODIPY: Bifunctional reporter for hybrid optical/positron emission tomography imaging
-
The best of both worlds: BODIPY-based imaging probes can be tracelessly transformed into hybrid PET/fluorescence imaging reagents by direct 19F/18F exchange without the need for redesign. This approach has the potential to accelerate
- Hendricks, J. Adam,Keliher, Edmund J.,Wan, Dongpeng,Hilderbrand, Scott A.,Weissleder, Ralph,Mazitschek, Ralph
-
-
Read Online
- Substitutedmeso-vinyl-BODIPY as thiol-selective fluorogenic probes for sensing unfolded proteins in the endoplasmic reticulum
-
A new type of thiol probes based on themeso-vinyl-BODIPY (VB) scaffold were developed. The monochloro-substitutedVB1Clexhibited the largest fluorescence enhancement (>200-fold) as well as high selectivity upon biological thiol sensing.VB1Clwas successfully applied for reporting the protein unfolding process under ER stress in living cells.
- Mu, Huiying,Miki, Koji,Kubo, Takuya,Otsuka, Koji,Ohe, Kouichi
-
-
Read Online
- Modulating absorption and charge transfer in bodipy-carbazole donor-acceptor dyads through molecular design
-
Three bodipy-based (BDP = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) donor-acceptor dyads were designed and synthesized, and their ground-state and photophysical properties were systematically characterized. The electronic coupling between the BDP chromophore and an electron-donating carbazole (Carb) moiety was tuned by attachment via the meso and the beta positions on the BDP core, and through the use of various chemical linkers (phenyl and alkynyl) to afford mesoBDP-Carb, mesoBDP-phen-Carb, and betaBDP-alk-Carb. meso-Substituted dyads were found to retain ground-state absorption features of the unsubstituted BDP. However, variation of the linkage between the donor and acceptor moieties modulated the photophysical behavior of excited-state deactivation by controlling the rate of photoinduced internal charge transfer (ICT). The beta-substituted dyad dramatically tuned (red shifted) the absorption spectrum, while retaining desired features of the BDP, specifically stability and high extinction coefficients, however the ICT kinetics were accelerated compared to the meso-substituted dyads. Density functional theory (DFT) and time-dependent DFT (TDDFT) were carried out on the six potential dyads formed between BDP and Carb (attachment using the beta and meso positions for all three connections: direct, phenyl and alkynyl) to support the experimental observations. DFT and TDDFT showed molecular orbital density spread across the HOMO level only when attachment occurred through the beta position of BDP. In the meso-substituted BDP-Carb dyads, the molecular orbitals resembled those of the unsubstituted BDP. This work reveals several possible synthetic paradigms to tune photophysical properties with directed synthetic modifications and provides a mechanistic understanding of the ground- and excited- state behavior in these small-molecule donor-acceptor dyads.
- Strahan, John,Popere, Bhooshan C.,Khomein, Piyachai,Pointer, Craig A.,Martin, Shea M.,Oldacre, Amanda N.,Thayumanavan,Young, Elizabeth R.
-
-
Read Online
- A BODIPY boronium cation for the sensing of fluoride ions
-
In the presence of iodide ions, the cationic p-dimethylaminopyridine adduct of 1,3,5,7,8-pentamethylpyrromethene-boron fluoride [1-DMAP]+ reacts with fluoride ions to afford the corresponding brightly fluorescent difluoride 1-F. The Royal Society of Chemistry.
- Hudnall, Todd W.,Gabbai, Francois P.
-
-
Read Online
- A photosensitizer molecule and its application in improving tumor retention time to enhance large-volume tumor treatment
-
The present invention discloses a photosensitizer molecule and its application in improving tumor retention time to enhance the treatment of large-volume tumors, belonging to the field of nanomaterials. The present invention synthesizes AN-BDP by introducing anthracene into the BODIPY-meso bit. Due to the strong intermolecular π-π interaction of anthracene, AN-BDP and DSPE-PEG2000, a copolymer with amphiphilic block, self-assemble into stable nanoparticles AN-BDP NPs. In addition, anthracene can also enable AN-BDP to be excited to a triple excited state under light exposure and produce 1O2 under the action ofO2 。 An-BDP NPs are enriched at the tumor site and retained for ~10 days. In mouse tumor models of conventional volume size, AN-BDP NPs can completely inhibit tumor growth with one light therapy with a tail vein injection. In the large-volume tumor model, only 12% of tumor growth inhibition rates were observed under the same treatment conditions. Due to the long tumor retention time, a single injection of AN-BDP NPs can be used for 3 light therapy, and the treatment effect is significantly improved.
- -
-
Paragraph 0040-0043
(2022/01/08)
-
- Fine-Tuning Plasmon-Molecule Interactions in Gold-BODIPY Nanocomposites: The Role of Chemical Structure and Noncovalent Interactions
-
Strong coupling between localized surface plasmons and molecular absorptions leads to remarkable changes in the photophysical properties of dye-loaded metal nanoparticles. Here, we report supramolecular nanocomposites consisting of BODIPY, tryptophan, and gold nanoparticles, and investigate the effect of structural variations on their photophysical properties. Our results indicate that the photostability and photosensitization properties of the nanocomposites depend on the chemical composition of the BODIPY molecules. The singlet oxygen quantum yield of the nanocomposites NC1 (BODIPY, B1 bearing a single methyl group) and NC3 (BODIPY, B3 with 5 methyl and 2 iodo groups) were 0.46 and 0.42, respectively, which were significantly higher compared to their individual components. Ultrafast spectroscopy studies revealed that the migration of photoexcited BODIPY electrons to the plasmonic photoexcitation allowed electron transfer into the singlet oxygen states, thereby leading to efficient generation of singlet oxygen.
- Kumar, P. P. Praveen,Rahman, Atikur,Goswami, Tanmay,Ghosh, Hirendra N.,Neelakandan, Prakash P.
-
-
- Design and synthesis of perfluoroalkyl decorated BODIPY dye for random laser action in a microfluidic device
-
New and highly emissive 2,6-diacetynyl and 2,6-bis-(phenylacetynyl) functionalized pentamethyldifluoroboron-dipyrromethane (BODIPY) derivatives (FBDP1-2) with perfluorinated pendant groups at the boron center have been synthesized successfully by the combination of two strategies: extending the π-conjugation and functionalization at the boron centre. The newly synthesized dyes have been characterized unambiguously by using various analytical tools such as multinuclear NMR, MALDI-TOF, and single crystal XRD analysis. The dyes (FBDP1-2) exhibit excellent photophysical properties in the yellow to red spectral region (λabs = 530 nm and 555 nm, and λem = 555 nm and 596 nm, respectively) with relatively good Stokes shifts (849 cm-1 and 1240 cm-1), high quantum efficiency (?F = 0.72 and 0.61) and excellent brightness (2.95 × 104 and 2.38 × 104 M-1 cm-1). Most importantly, under a transverse pumping condition at 532 nm, the dyes show efficient and stable laser action, having a good tunable range (20 nm and 13 nm) with a maximum lasing efficiency of 45% and 38% for FBDP1 and FBDP2, respectively. Moreover, the random lasing behavior of FBDP1 has been investigated in a dye-circulated polydimethylsiloxane (PDMS) based disordered microfluidic device. The appearance of randomly positioned sharp spikes with a full width at half maximum (FWHM) of less than 0.3 nm around 555 nm indicates the random laser (RL) emission. The relationship between input pump energy and output random lasing intensity has also been demonstrated, with the random lasing threshold of 0.5 mJ.
- Maity, Apurba,Sarkar, Anirban,Bhaktha B.n, Shivakiran,Patra, Sanjib K.
-
supporting information
p. 14650 - 14661
(2020/10/02)
-
- Phenylethynyl BODIPY fluorescent dichroic liquid crystal compounds and application thereof
-
The invention discloses phenylethynyl BODIPY fluorescent dichroic liquid crystal compounds and application thereof. The compounds have a structure as shown in a general formula M which is described inthe specification. In the general formula M, n is equal to 0 or 1; and R is one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group, an n-heptyl and an n-octyl group. According to the invention, BODIPY is used as a parent body; a phenylacetylene rigid structure is introduced to the position 2 through a Sonogashira coupling reaction, and a bicyclohexane flexible polycyclic ring reacts with the parent body through an esterification reaction and the Sonogashira coupling reaction; so a series of phenylethynylBODIPY fluorescent dichroic liquid crystal compounds are designed and synthesized. The compounds disclosed by the invention have the maximum absorption wavelength of 526 nm and the maximum emission wavelength of 567 nm in dichloromethane, shows red fluorescence, has a liquid crystal phase at 145-185 DEG C, and shows a good dichroic ratio and ordered parameters in liquid crystal E7.
- -
-
Paragraph 0038-0042
(2020/02/29)
-
- Effect of Substituents on the Photophysical Properties and Bioimaging Application of BODIPY Derivatives with Triphenylamine Substituents
-
We investigated the intramolecular charge transfer characteristics in the S1 state of boron-dipyrromethene (BODIPY) derivatives with triphenylamine (TPA) substituents, depending on the substituted position and the number of substituents. Based on the spectroscopic and theoretical results, the β-substitution of TPA on BODIPY hybridizes locally excited and intramolecular charge transfer characteristics in the S1 state because of strong coupling between the highest occupied molecular orbitals of BODIPY and TPA moieties, and consequently, the BODIPY derivatives with β-substituted TPAs exhibit strong red-color fluorescence around 640 nm in nonpolar and moderately polar solvents. The TPA substituent with propeller-like nonplanar geometry could prevent H-type aggregation between neighboring BODIPY derivative units and induce aggregation-induced emission enhancement (AIEE) characteristics of the BODIPY derivatives with TPA substituents, which are helpful to maintain their emission efficiencies under highly concentrated and condensed conditions. Since the red-color emission and AIEE property of the BODIPY derivatives with β-substituted TPAs are promising characteristics for a bioimaging application, we applied these derivatives to L-929 fibroblast cells for cellular imaging. The BODIPY derivative with a single β-substituted TPA (compound 2) was effectively loaded into porous silica nanoparticles (SNPs). Consequently, we achieved good cellular uptake of 2-SNPs and good cellular imaging, which further confirmed the bioimaging ability of 2-SNPs.
- Bui, Hoa Thi,Mai, Duy Khuong,Kim, Boram,Choi, Kyong-Hoon,Park, Bong Joo,Kim, Ho-Joong,Cho, Sung
-
p. 5601 - 5607
(2019/08/30)
-
- With metal nickel catalyzed C - X of the key is formed organic photosensitizer and its synthetic method (by machine translation)
-
The invention discloses a formed metal nickel catalyzed C - X key organic photosensitizer and its synthetic method, wherein X represents C, O or N, the organic photosensitizer to common beryllium two pyrrole (BODIPY) as the skeleton, in the boron atom or skeleton is introduced on the aromatic group, derived from one kind has superior light oxidation-reduction properties of the organic photosensitizer. Compared with the literature reports of expensive metal ruthenium or iridium photosensitizer, these novel organic photosensitizer has the advantages of simple synthesis, the price is cheap, consumption is low, and the obvious advantages of heavy metal. It is particularly important, under the condition of no external ligand, [...] of the photosensitizer can be formed with the metal nickel catalyzed C - C, C - O and C - N and other important chemical bond, has important application value. (by machine translation)
- -
-
Paragraph 0025; 0026
(2018/09/11)
-
- Quantitative Profiling of the Heavy-Atom Effect in BODIPY Dyes: Correlating Initial Rates, Atomic Numbers, and 1O2 Quantum Yields
-
Direct oxidation using molecular oxygen is both attractive and atom-efficient. However, this process first requires the catalyst-based activation or electronic reconfiguration of inert O2. The most expedient strategy relies on the generation of singlet oxygen (1O2; a1Δg) from the triplet state (3O2; X3Σg–) by a photosensitizer. In the current arsenal of photosensitizers, boron-dipyrromethene (BODIPY) cores are considered privileged on account of their unique photophysical characteristics and the ability to tune their behavior through facile structural modifications such as halogen (X) incorporation. Thus, the scaffold has become synonymous with the renowned heavy-atom effect (HAE), a phenomenon that correlates the increasing atomic number (ZX) of pendant halogen atoms with an enhanced probability of intersystem crossing (S1→T1). Herein, a facile GC-based method to assess catalyst performance has been developed and validated with a focused set of halogenated BODIPY scaffolds. An initial-rate approximation was applied to a model transformation and follows the HAE trend (v0,H 0,Cl 0,Br 0,I). This operationally simple approach was corroborated by complementary determinations of absolute singlet oxygen and photoluminescence quantum yields and time-resolved luminescence decays to evaluate lifetimes. For double logarithmic plots, linear correlations between relative intersystem-crossing rates kXisc/kYisc and relative atomic numbers ZX/ZY for the respective substituents with corresponding slopes of approximately 4 were obtained, that is, kisc ~ Z4, which also was shown to hold for the fluorescence-lifetime-corrected singlet-oxygen quantum yields as independent measurements. This substantiates theoretical predictions pertaining to the heavy-atom effect.
- Rey, Yannick P.,Abradelo, Dario G.,Santschi, Nico,Strassert, Cristian A.,Gilmour, Ryan
-
p. 2170 - 2178
(2017/04/24)
-
- Synthesis, photophysical and concentration-dependent tunable lasing behavior of 2,6-diacetylenyl-functionalized BODIPY dyes
-
2,6-Diacetylenyl- and 2,6-bis(arylacetylenyl)-functionalized pentamethyl-difluoroborondipyrromethene (BODIPY) derivatives, namely, PBDP1 and PBDP2-4 (aryl = phenyl, 4-methoxyphenyl, or 4-cyanophenyl), respectively, which exhibit extended π-conjugation, were synthesized and characterized by various spectroscopic methods. Significant bathochromic shifts in both absorption and emission were observed upon modifying the structure of the BODIPY core via the strategy of extending its π-conjugation. The derivatives displayed efficient emission in the yellow-to-red spectral region, with a high fluorescence quantum yield and a relatively large Stokes shift. Under conditions of transverse pumping in a cuvette, PBDP1 and PBDP2 exhibited highly efficient and stable laser activity for up to 180 and 110 minutes of continuous irradiation, respectively. Amplified spontaneous emission (FWHM of ca. 2.5 nm) with an efficiency of 41% and 36% was achieved for PBDP1 and PBDP2, respectively, in toluene, which had tunable ranges of 561 to 580 nm and 602 to 617 nm, respectively, on irradiation with a Q-switched Nd:YAG laser at 532 nm. The lasing properties of PBDP3 and PBDP4, which contain electron-donating (-OMe) and electron-withdrawing (-CN) arylacetylenyl moieties, respectively, were also investigated. A corresponding digold(i) diacetylide organometallic complex, namely, (PPh3)Au-C≡C-BODIPY-C≡C-Au(PPh3) (PBDP5) was also synthesized and characterized to study the effect of Au(i). PBDP5 exhibited phosphorescence in the vis-NIR region centered at 751 nm at 77 K owing to heavy-atom-induced intersystem crossing.
- Maity, Apurba,Sarkar, Anirban,Sil, Amit,B. N., Shivakiran Bhaktha,Patra, Sanjib K.
-
supporting information
p. 2296 - 2308
(2017/03/22)
-
- Influence of Ester versus Amide Linkers on the Supramolecular Polymerization Mechanisms of Planar BODIPY Dyes
-
We report the H-type supramolecular polymerization of two new hydrophobic BODIPY derivatives equipped with ester and amide linkages. Whereas the ester-containing BODIPY derivative undergoes an isodesmic supramolecular polymerization in which the monomers are parallel-oriented, the replacement of the ester by amide groups leads to a highly cooperative self-assembly process into H-type aggregates with a rotational displacement of the dye molecules within the stack. The dye organization imposed by simultaneous π–π and hydrogen bonding interactions is the driving force for the cooperative supramolecular polymerization, whereas the absence of additional hydrogen bonds for the ester-containing moiety does not suffice to induce cooperative phenomena.
- R?dle, Alexander,Ritschel, Benedikt,Mück-Lichtenfeld, Christian,Stepanenko, Vladimir,Fernández, Gustavo
-
supporting information
p. 15772 - 15777
(2016/10/24)
-
- DYE COMPRISING PYRROMETHENE BORON COMPLEX COMPOUND
-
The present invention relates to a dye comprising a pyrromethene boron complex compound. The dye comprising a pyrromethene boron complex according to the present invention does not have fluorescence, has excellent light resistance, and absorbs light of a specific wavelength, thereby being used as a display dye.COPYRIGHT KIPO 2016
- -
-
Paragraph 0074-0077
(2016/10/17)
-
- Masking and demasking strategies for the BF2-BODIPYs as a tool for BODIPY fluorophores
-
An efficient and chemoselective route for transforming BF2-BODIPYs to Et2B-BODIPYs (masking) was developed using Et2AlCl. The Et groups can be easily replaced with F atoms using BF3·Et2O in moist CH2Cl2 to regenerate the BF2-BODIPYs (demasking). The masking-demasking strategy is very useful for synthesizing functionalized BODIPYs via nucleophilic and reductive reactions. The masking strategy was used to synthesize a BODIPY dimer by McMurry coupling of a formyl Et2B-BODIPY, while a new BODIPY with an asymmetrically substituted B-center was synthesized using the demasking strategy.
- More, Ankush B.,Mula, Soumyaditya,Thakare, Shrikant,Sekar, Nagaiyan,Ray, Alok K.,Chattopadhyay, Subrata
-
p. 10981 - 10987
(2015/01/08)
-
- Synthesis and transformations of 5-chloro-2,2′-dipyrrins and their boron complexes, 8-chloro-BODIPYs
-
Symmetric dipyrrylketones 1a,b were synthesized in two steps from the corresponding α-free pyrroles, by reaction with thiophosgene followed by oxidative hydrolysis under basic conditions. The dipyrrylketones produced the corresponding 5-chloro-dipyrrinium salts or 5-ethoxy-dipyrrins on reaction with phosgene or Meerwein's salt, respectively. Boron complexation of the dipyrrins afforded the corresponding 8-functionalized BODIPYs (borondipyrromethenes) in high yields. The 5-chloro-dipyrrinium salts reacted with methoxide or ethoxide ions to produce monopyrrole esters, presumably via a 5,5-dialkoxy-dipyrromethane intermediate. In contrast, 8-chloro-BODIPYs underwent a variety of nucleophilic substitutions of the chloro group in the presence of alkoxide ions, Grignard reagents, and thiols. In the presence of excess alkoxide or Grignard reagent, at room temperature or above, substitution at the boron center also occurred. The 8-chloro-BODIPY was a particularly useful reagent for the preparation of 8-aryl-, 8-alkyl-, and 8-vinyl-substituted BODIPYs in very high yields, using Pd0-catalyzed Stille cross-coupling reactions. The X-ray structures of eleven BODIPYs and two pyrroles are presented, and the spectroscopic properties of the synthesized BODIPYs are discussed.
- Wang, Haijun,Vicente, M. Graca H.,Fronczek, Frank R.,Smith, Kevin M.
-
p. 5064 - 5074
(2014/05/06)
-
- H-aggregates of oligophenyleneethynylene (OPE)-BODIPY systems in water: Guest size-dependent encapsulation mechanism and co-aggregate morphology
-
The synthesis of a new oligophenyleneethynylene (OPE)-4,4-difluoro-4-bora- 3a,4a-diaza-s-indacene (BODIPY) bolaamphiphile 1 and its aqueous self-assembly are reported. Compound 1 forms H-type aggregates in aqueous and polar media, as demonstrated by UV/Vis and fluorescence experiments. Concentration-dependent 1H NMR studies in CD3CN reveal that the BODIPY units are arranged on top of each other into π-stacks with H-type excitonic coupling, as supported by ROESY NMR and theoretical calculations and visualized by Cryo-SEM studies. A detailed analysis of the spectral changes observed in temperature-dependent UV/Vis studies reveals that 1 self-assembles in a non-cooperative (isodesmic) fashion in water. The hydrophobic interior of these self-assembled structures can be exploited to encapsulate hydrophobic dyes, such as tetracene and anthracene. Both dyes absorb in a complementary region of the UV/Vis spectrum and are small enough to interact with the hydrophobic segments of 1. Temperature-dependent UV/Vis studies reveal that the spectral changes associated to the encapsulation mechanism of tetracene can be fitted to a Boltzmann function, and the initially flexible fibres of 1 rigidify upon guest addition. In contrast, the co-assembly of 1 and anthracene is a highly cooperative process, which suggests that a different class of (more-ordered) aggregates is formed. TEM and Cryo SEM imaging show the formation of uniform spherical nanoparticles, indicating that a subtle change in the guest molecular structure induces a significant change in the encapsulation mechanism and, consequently, the aggregate morphology. Dye encapsulation: We report the aqueous self-assembly of a new oligophenyleneethynylene (OPE)-BODIPY amphiphilic derivative into H-type aggregates and its ability to encapsulate hydrophobic guest molecules. Subtle changes in the guest size induce a dramatic change of the encapsulation mechanism. Addition of tetracene leads to the non-cooperative formation of stiff fibres, whereas co-assembly with anthracene is a highly cooperative process, leading to highly organized micellar assemblies.
- Allampally, Naveen Kumar,Florian, Alexander,Mayoral, Maria Jose,Rest, Christina,Stepanenko, Vladimir,Fernandez, Gustavo
-
supporting information
p. 10669 - 10678
(2014/11/07)
-
- Two fluorescent 2,6-substituted pyridyl boron-dipyrromethene dyes for selective sensing of cuprous ions
-
Two new pyridine-substituted boron-dipyrromethene (BODIPY) dyes have been synthesized via the Suzuki coupling reactions of 2,6-diiodo-1,3,5,7-tetramethyl- 8-methyl-4,4-difluoroboradiazaindacene and respective pyridinylboronic acid. The molecular structures of the two title compounds have been determined by single-crystal X-ray diffraction analyses. The absorption and steady-state fluorescent properties in different solvents were investigated, which showed that the two compounds are highly fluorescent with a relatively small Stokes shift, high fluorescent quantum yields and little solvent dependence, similar to other BODIPY chromophores. The fluorescence of two compounds were highly sensitive towards Cu+, owing to significant interactions between Cu+ and the nitrogen atoms on the pyridine rings.
- Zhou, Lian,Zhu, Cheng-Cheng,Xue, Yun-Shan,He, Wei-Jiang,Du, Hong-Bin,You, Xiao-Zeng,Li, Yi-Zhi
-
p. 355 - 359
(2013/10/08)
-
- Linear oligofluorene-BODIPY structures for fluorescence applications
-
A family of linear oligofluorene-BODIPY structures, containing either a ter- or quaterfluorene unit, have been prepared, in which the attachment of the oligofluorene chain to the BODIPY unit is switched between the meso- and beta-positions. Each member of this family was investigated by UV-vis absorption and photoluminescence spectroscopy, cyclic voltammetry and thermal studies (TGA and DSC) to determine their suitability as emissive layers in hybrid luminescent devices. One candidate was then successfully deployed as a down converter to convert UV to visible light.
- Findlay, Neil J.,Orofino-Pena, Clara,Bruckbauer, Jochen,Elmasly, Saadeldin E. T.,Arumugam, Sasikumar,Inigo, Anto R.,Kanibolotsky, Alexander L.,Martin, Robert W.,Skabara, Peter J.
-
p. 2249 - 2256
(2013/05/22)
-
- Alternated stacks of nonpolar oligo(p-phenyleneethynylene)-BODIPY systems
-
Supramolecular chemistry: The self-assembly of an oligo(p- phenyleneethynylene)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (OPE-BODIPY) system into alternated 1D π stacks in solution exhibited liquid-crystalline properties at room temperature. This system represents a new approach towards a controlled dye organization exclusively driven by π-π interactions (see figure). Copyright
- Florian, Alexander,Mayoral, María José,Stepanenko, Vladimir,Fernández, Gustavo
-
supporting information
p. 14957 - 14961
(2013/01/15)
-
- Multimodal and multifunctional stealth polymer nanospheres for sustained drug delivery
-
We report the preparation of fluorescent and magnetic PMMA nanospheres, and a corresponding PEGylated 'stealth' analogue prepared using a block copolymer. The nanospheres contain encapsulated magnetite nanoparticles and fluorescent BODIPY dyes, including a new such dye with pH-sensitive fluorescent emission. The new dye could potentially be used as an indicator of the immediate physiological environment. The nanospheres were non-toxic at up to 500 μg ml-1 in PC12 cells. Lomerizine, a lipophilic calcium channel blocker, was also encapsulated in the nanospheres and displayed sustained, pH-dependent release characteristics. The nanospheres may be of use to release lomerizine and other water-insoluble drugs at central nervous system injury sites. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012.
- Evans, Cameron W.,Latter, Melissa J.,Ho, Diwei,Peerzade, Saquib Ahmed M. A.,Clemons, Tristan D.,Fitzgerald, Melinda,Dunlop, Sarah A.,Iyer, K. Swaminathan
-
scheme or table
p. 1457 - 1462
(2012/07/30)
-
- BODIPY dyes with β-conjugation and their applications for high-efficiency inverted small molecule solar cells
-
Small molecule BODIPY dyes incorporating conjugated substituents at the β sites have been synthesized. Solution processed inverted bulk heterojunction cells were fabricated from the blends of the dyes and PC 71BM. The cells exhibited very high open-circuit voltages (>0.9 V) and a high conversion efficiency of 3.22% has been achieved.
- Lin, Hsin-Yu,Huang, Wei-Ching,Chen, Yung-Chung,Chou, Hsien-Hsin,Hsu, Chih-Yu,Lin, Jiann T.,Lin, Hao-Wu
-
supporting information
p. 8913 - 8915
(2012/11/07)
-
- Synthesis, photophysical, electrochemical, and electrogenerated chemiluminescence studies. multiple sequential electron transfers in BODIPY monomers, dimers, trimers, and polymer
-
Synthesis of the C8 BODIPY monomers, dimers, and trimers, a C8 polymer, and N8 aza-BODIPY monomer and dimer was carried out. Methyl and mesityl C8-substituted monomers, dimers, and trimers were used. Dimers, trimers, and polymer were formed chemically through the β-β (2/6) positions by oxidative coupling using FeCl3. A red shift of the absorbance and fluorescence is observed with addition of monomer units from monomer to polymer for C8 dyes. The aza-BODIPY dye shows red-shifted absorbance and fluorescence compared with the C8 analogue. Cyclic voltammetry shows one, two, and three one-electron waves on both reduction and oxidation for the monomer, dimer, and trimer, respectively, for the C8 BODIPYs. The separation for the reduction peaks for the C8 dimers is 0.12 V compared with 0.22 V for the oxidation, while the trimers show separations of 0.09 V between reduction peaks and 0.13 V for oxidation peaks. The larger separations between the second and third peaks, 0.25 V for the oxidation and 0.2 V for the reduction, are consistent with a larger energy to remove or add a third electron compared with the second one. The BODIPY polymer shows the presence of many sequential one-electron waves with a small separation. These results provide evidence for significant electronic interactions between different monomer units. The aza-BODIPY dye shows a reduction peak 0.8 V more positive compared to the C8 compound. Aza-BODIPY dimer shows the appearance of four waves in dichloromethane. The separation between two consecutive waves is around 0.12 V for reduction compared with 0.2 V for oxidation, which is comparable with the results for the C 8 dyes. Electrogenerated chemiluminescence (ECL) of the different species was obtained, including weak ECL of the polymer.
- Nepomnyashchii, Alexander B.,Broering, Martin,Ahrens, Johannes,Bard, Allen J.
-
p. 8633 - 8645
(2011/07/29)
-
