121207-31-6Relevant articles and documents
Bright solid-state red-emissive BODIPYs: facile synthesis and their high-contrast mechanochromic properties
Duan, Chong,Zhou, Yibin,Shan, Guo-Gang,Chen, Yuncong,Zhao, Weijun,Yuan, Dandan,Zeng, Lintao,Huang, Xiaobo,Niu, Guangle
, p. 3471 - 3478 (2019)
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.
Exploring the Application of the Negishi Reaction of HaloBODIPYs: Generality, Regioselectivity, and Synthetic Utility in the Development of BODIPY Laser Dyes
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.
, p. 3700 - 3710 (2016)
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.
Synthesis of [18F]BODIPY: Bifunctional reporter for hybrid optical/positron emission tomography imaging
Hendricks, J. Adam,Keliher, Edmund J.,Wan, Dongpeng,Hilderbrand, Scott A.,Weissleder, Ralph,Mazitschek, Ralph
, p. 4603 - 4606 (2012)
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
Modulating absorption and charge transfer in bodipy-carbazole donor-acceptor dyads through molecular design
Strahan, John,Popere, Bhooshan C.,Khomein, Piyachai,Pointer, Craig A.,Martin, Shea M.,Oldacre, Amanda N.,Thayumanavan,Young, Elizabeth R.
, p. 8488 - 8501 (2019)
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.
Fine-Tuning Plasmon-Molecule Interactions in Gold-BODIPY Nanocomposites: The Role of Chemical Structure and Noncovalent Interactions
Kumar, P. P. Praveen,Rahman, Atikur,Goswami, Tanmay,Ghosh, Hirendra N.,Neelakandan, Prakash P.
, p. 87 - 94 (2020/10/19)
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.
Design and synthesis of perfluoroalkyl decorated BODIPY dye for random laser action in a microfluidic device
Maity, Apurba,Sarkar, Anirban,Bhaktha B.n, Shivakiran,Patra, Sanjib K.
supporting information, p. 14650 - 14661 (2020/10/02)
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.