State of the Art of Bodipy‐Based Photocatalysts in Organic Synthesis

Bonfils, Paul De; Péault, Louis; Nun, Pierrick; Coeffard, Vincent

doi:10.1002/ejoc.202001446

Cited by 72 publications

(56 citation statements)

References 122 publications

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“…These results not only show that the organic triplet PSs can be used as photocatalysts for synthetic organic reactions, but actually these compounds are much more efficient than the traditional triplet PSs (i.e., Ir(ppy) 3 or Ru(bpy) 3 Cl 2 ). Considering the feasibility of preparation of such C 60 -organic chromophore dyads, the robust chemo- and photostability, the tunable photophysical and redox properties, further development of the C 60 -organic chromophore dyads as an efficient photocatalyst is promising …”

Section: Triplet Photosensitizers Showing Strong Absorption Of Visibl...mentioning

confidence: 92%

“…Considering the feasibility of preparation of such C 60 -organic chromophore dyads, the robust chemo-and photostability, the tunable photophysical and redox properties, further development of the C 60 -organic chromophore dyads as an efficient photocatalyst is promising. 18 H 2 evolution by photocatalysis is one of the most investigated topics of sustainable energy source. One typical method is to drive an electron transfer to the reduction reaction center (reduction catalyst), such as Co 3+ complexes (e.g., cobaloxime complexes) with the photocatalysts (very often a triplet PS, concerning the molecular photocatalysis).…”

Section: −•mentioning

confidence: 99%

“…In recent years, photocatalysis and photovoltaics have attracted much attention to address the challenges of sustainable energy or environmentally benign chemical production. Among others, the photocatalytic H 2 evolution by splitting of water, − CO 2 photoreduction, − photodynamic therapy (PDT), , and the photoredox catalytic organic synthetic reaction are of particular interest. − These efforts will supply green energy materials by using solar light or will reduce pollution and increase the atomic economics in preparation of highly versatile organic compounds. These areas very often share similar catalysts, i.e., the triplet photosensitizers (PSs).…”

Section: Introductionmentioning

confidence: 99%

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Triplet Photosensitizers Showing Strong Absorption of Visible Light and Long-Lived Triplet Excited States and Application in Photocatalysis: A Mini Review

et al. 2021

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Triplet photosensitizers (PSs) have been studied as photocatalysts in photocatalytic H2 evolution by water splitting and photoredox catalytic synthetic organic reactions, etc. The applications share common features that the photocatalysts (triplet PSs) harvest the photoexcitation energy, then undergo intersystem crossing (ISC), and finally initiate the electron transfer or triplet energy transfer, which are intermolecular processes in most cases. Thus, triplet PSs showing a strong visible-light-harvesting ability and long triplet excited state lifetimes are desired because they can enhance the above intermolecular processes. The conventional transition metal complexes (i.e., Ru(bpy)3X2 or Ir(ppy)3) have been widely used; however, these complexes are not satisfactory due to their weak absorption of visible light and short triplet excited state lifetimes. To a large extent, the photophysical property of these complexes is due to the low-lying metal-to-ligand charge transfer (MLCT) state, the S0 → 1MLCT transition is weakly allowed, and a strong heavy atom effect exists for the 3MLCT state, which results in weak visible light absorption and a short triplet excited state lifetime, respectively. This mini review introduces the recent progress of the development of the transition metal complexes as well as the organic triplet PSs that show a strong visible-light-harvesting ability and long triplet excited state lifetimes. The application of these new triplet PSs in photocatalytic H2 evolution and photoredox catalytic synthetic organic reactions is summarized.

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Section: Triplet Photosensitizers Showing Strong Absorption Of Visibl...mentioning

confidence: 92%

Section: −•mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Triplet Photosensitizers Showing Strong Absorption of Visible Light and Long-Lived Triplet Excited States and Application in Photocatalysis: A Mini Review

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“…It is also known that BODIPYs have an electron-deficient nature, 17 making them susceptible to act as an oxidant. 18 The use of BODIPYs as a PC has already been explored and reviewed 19 by other authors. For example, Huang and Zhao 20 reported the dehydrogenative coupling of tetrahydroquinolines with nitroalkanes using diiodinated BODIPY 1 as PC (Scheme 1a).…”

Section: ■ Introductionmentioning

confidence: 99%

“…The use of BODIPYs as a PC has already been explored and reviewed by other authors. For example, Huang and Zhao reported the dehydrogenative coupling of tetrahydroquinolines with nitroalkanes using diiodinated BODIPY 1 as PC (Scheme a).…”

Section: Introductionmentioning

confidence: 99%

Dibromo-BODIPY as an Organic Photocatalyst for Radical–Ionic Sequences

et al. 2021

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A new dibrominated 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) is reported as a new metal-free photocatalyst. This BODIPY showed similar optoelectronic, electrochemical, and performance properties to those of Ru(bpy)3Cl2, one of the most common photocatalysts in a known radical–ionic transformation, such as the formation of 1,4-dicarbonyl compounds. Moreover, additional sequences in which the generated oxonium ion is trapped by an internal nucleophile were developed using this BODIPY photocatalyst. These new sequences allowed the straightforward preparation of γ-alkoxylactones, monoprotected 1,4-ketoaldehydes, and dihydrofurans. This new catalyst, the methodology, and the forged functional groups could be important tools in organic synthesis.

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An Unexpected Boron Rearrangement Leads to a Fluorogenic and Colorimetric BODIPY Probe

Merkes

Raabe

Kießling

et al. 2023

Advanced Optical Materials

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addition of hydroboranes to 2-methylbut-2-ene, the newly formed (3-methylbut-2-yl)borane undergoes a migration of BR 2 (or BI 2 ) at 150 °C. More recently Arnold observed a net trialkyl borane (BR 3 ) transfer in the reduction of β-ketoimidazolium (Rki) using NaHBEt 3 or KHBEt 3 . [8] In this reaction the formed boronic intermediate (Rki-O-BEt 3 ) undergoes a migration of a triethylboron (BEt 3 ) group to either the imidazole carbon (C2 or C3) or nitrogen, (i.e., C-BEt 3 or N-BEt 3 type bond formations) depending on the N-substituent and temperature, yielding "abnormal" carbene-borane adducts. In 2017, Aggarwal reported a net boron pinacolate migration in the reaction of ortho-lithiated benzylic amines with boronic esters. [9] This reaction proceeds via a Lewis acid catalyzed 1,3-borotropic shift of the dearomatized arylboronate intermediate. To the best of our knowledge, there are no descriptions involving rearrangements of difluoroborane (BF 2 ) or BR 2 in heterocyclic compounds.Since their first discovery by Treibs and Kreuzer, [10] 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyes have been the subject of a vast number of research studies, ranging from life sciences [11] to materials sciences [12] and photocatalysis. [13] The increasing interest in BODIPY and its derivatives is due to the high photostability and large fluorescence emission quantum yields.Our group has been actively working on expanding the scope of BODIPY chromophores for biomedical applications by introducing, for example, electron-rich pyrrols to prepare quencher dyes, [14] reactive phenolic groups to detect short-lived species [15] and isoatomic substitution to tune the optical properties. [16] For further development of BODIPYs for trigger-responsive applications, we were intrigued by an alternative BF 2 -complexation. [17] This led to the isolation of a kinetically stable chromophore with a BF 2 -chelation to oxygen (O)-, and nitrogen (N) (oxadiazaborinine). To our surprise, this oxadiazaborinine can undergo a boron to nitrogen rearrangement (O-[BF 2 ]-N to N-[BF 2 ]-N) to generate a BODIPY chromophore. We report the synthesis, characterization, and mechanistic aspects of the new boron rearrangement and the possible time-temperature indicator (TTI) application.TTIs are temperature history indicators and are used for temperature control. Temperature control is crucial for maintaining the quality of perishable chilled and frozen products, including foods, pharmaceuticals, chemicals, and vaccines. In the distribution chain, temporary increases in temperature can adversely affect the quality of the cooled or frozen products. The detection of these incidents, classified as "temperatureThe isolation and characterization of a kinetically stable oxadiazaborinine (ODB) dye are described, which undergoes an unexpected thermal boron rearrangement with a color change and increase in fluorescence. This controllable reaction allows for the use as a practical time-temperature indicator probe with the advantages of photostability, non-reversi...

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State of the Art of Bodipy‐Based Photocatalysts in Organic Synthesis

Cited by 72 publications

References 122 publications

Triplet Photosensitizers Showing Strong Absorption of Visible Light and Long-Lived Triplet Excited States and Application in Photocatalysis: A Mini Review

Triplet Photosensitizers Showing Strong Absorption of Visible Light and Long-Lived Triplet Excited States and Application in Photocatalysis: A Mini Review

Dibromo-BODIPY as an Organic Photocatalyst for Radical–Ionic Sequences

An Unexpected Boron Rearrangement Leads to a Fluorogenic and Colorimetric BODIPY Probe

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