Generation of Triplet Excited States via Photoinduced Electron Transfer in <i>meso</i>-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro

Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M.; Savoie, Huguette; Flanagan, Keith J.; Sy, Cindy; Telitchko, Maxime; Laquai, Frédéric; Boyle, Ross W.

doi:10.1021/jacs.7b00551

Cited by 285 publications

(316 citation statements)

References 26 publications

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“…Note that in the TICS state,anegatively charged BODIPY radical will form upon the complete charge transfer from the amino group to the BODIPY scaffold. [13] This is in good agreement with our observation. [13] This is in good agreement with our observation.…”

supporting

confidence: 93%

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

et al. 2019

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Charge transfer and separation are important processes governing numerous chemicalreactions.Fundamental understanding of these processes and the underlying mechanisms is critical for photochemistry.H erein, we report the discovery of anew charge-transfer and separation process, namely the twisted intramolecular charge shuttle (TICS). In TICS systems,t he donor and acceptor moieties dynamically switch roles in the excited state because of an approximately 908 8 intramolecular rotation. TICS systems thus exhibit charge shuttling.T ICSs exist in several chemical families of fluorophores (sucha sc oumarin, BODIPY,a nd oxygen/carbon/ silicon-rhodamine), and could be utilized to construct functional fluorescent probes (i.e., viscosity-or biomoleculesensing probes). The discovery of the TICS process expands the current perspectives of charge-transfer processes and will inspire future applications.Photo-induced charge transfer and separation is af undamental process, [1] responsible for photosynthesis, [2] and has applications in solar cells, [3] photocatalysis, [4] and fluorescence probes. [5] Greater understanding of charge-transfer and separation processes is thus important to aid in improving photochemistry.H owever,o wing to fast photon-absorption rates and short excited state lifetime,u nderstanding charge transfer and separation at amolecular level remains asignificant challenge.This challenge could be overcome if the model systems under study emit fluorescence (or other forms of luminescence). [1b] Thec hanges in fluorescence output (for example, intensity,l ifetime,a nd wavelength) provide critical information on the thermodynamics and kinetics of the chargetransfer and separation processes in the excited state,a long with ap lethora of other important photo-physical and -chemical information. Accordingly,s tudies have been con-ducted to investigate charge-transfer and separation mechanisms in fluorescent compounds. [6] It has been widely known that the intramolecular charge transfer (ICT) could be modulated via adjusting the "push-pull" effect in acompound consisting of an electron-donating group (EDG) and/or an electron-withdrawing group (EWG). [7] In such compounds, ICT is further enhanced upon photoexcitation. In particular, in al andmark study,G rabowski and co-workers proposed that quasi-rigid donor-acceptor (D-A) compounds could undergo approximately 908 8 intramolecular twisting in the excited state,greatly reinforcing charge transfer and resulting in ac harge-separated state (D + -A À ). [8] They named this mechanism twisted intramolecular charge transfer (TICT; Figure 1a). Rationalization of the TICT mechanism [9] has greatly facilitated the development of many functional materials and devices,s uch as bright and photostable fluorophores, [10] dark quenchers, [11] viscosity sensors, [12] and polarity sensors. [6b] Notably,c harge-transfer and separation processes in both the ICT and TICT states are unidirectional, i.e., from the donor (D) to the acceptor (A) upon photoexcitation.In this study,w er...

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confidence: 93%

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

et al. 2019

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“…Preparation of 5,15-bis(3-acetoxyphenyl)-10,20-bis(4-fluoro-3nitrophenyl)porphyrin (19 Preparation of 10-(3-acetoxyphenyl)-5,15-bis(4-fluoro-3-nitrophenyl)corrole (20). Dipyrromethane 6 (1.14 g, 4.00 mmol, 2 equiv.)…”

Section: Preparation Of [515-bis(3-acetoxyphenyl)-1020-bis(345-trmentioning

confidence: 99%

“…The synthesized 4-amino-3-nitrophenyl-substituted dipyrromethanes were successfully applied in the synthesis BODIPYs and were tested in the synthesis of "trans"-A 2 B 2 porphyrins and A 2 B corroles. [19] Dipyrromethanes are of wide interest in organic synthesis and are commonly employed as building blocks for the selective synthesis of meso-substituted porphyrinoids as well as meso-substituted BODIPYs. apy (PDT).…”

Section: Introductionmentioning

confidence: 99%

“…: δ = 43.4 (C meso ), 107.9 (C pyrrole ), 108.9 (C pyrrole ), 112.5 (dd, J = 16.7, 5.0 Hz, Ar-C ortho ), 118.1 (C pyrrole ), 130.95 (C pyrrole ), 138.7 (q, J = 6.2 Hz, Ar-C ipso ), 138.8 (dt, J = 250.9, 15.3 Hz, Ar-C para ), 151.3 (ddd, J = 250.2, 10.0, 4.0 Hz, Ar-C meta ) ppm 19. F NMR (376 MHz, CDCl 3 ): δ = -162.40 (tt, J = 20.9, 6.4 Hz, 1 F, CF para ), -133.90 (dd, J = 20.8, 8.0 Hz, 2F, CF meta ) ppm.…”

mentioning

confidence: 99%

“…equiv.) They belong to the Ar 2 -C ipso and the Ar 2 -C nitro of the aryl residue 19. After the indicated time, DDQ (3.98 g, 17.52 mmol, 2 equiv., suspended in 50 mL of DCM) was added and stirred again under an argon atmosphere for 2.5 h at r.t. Triethylamine (1.21 mL, 8.76 mmol, 2 equiv.)…”

mentioning

confidence: 99%

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Synthesis of Porphyrinoids, BODIPYs, and (Dipyrrinato)ruthenium(II) Complexes from Prefunctionalized Dipyrromethanes

et al. 2019

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The introduction of functional groups into the meso‐position of dipyrromethanes, boron‐dipyrromethenes (BODIPYs) and porphyrinoids, is of fundamental importance in designing such dye systems for material sciences or photomedicine. One route that has proven to be particularly useful in this respect is the nucleophilic aromatic substitution (SNAr) on porphyrinoids and their precursors carrying electron‐withdrawing substituents. To further expand this methodology, the potential of the 4‐fluoro‐3‐nitrophenyl and the 3,4,5‐trifluorophenyl moieties for the synthesis of functionalized dipyrromethanes, BODIPYs, and porphyrinoids has been evaluated. The 3,4,5‐trifluorophenyl moiety proved not to be applicable in the SNAr with nucleophiles. The introduction of the 4‐fluoro‐3‐nitrophenyl group, however, allowed fast and efficient SNAr with various amine nucleophiles. The synthesized 4‐amino‐3‐nitrophenyl‐substituted dipyrromethanes were successfully applied in the synthesis BODIPYs and were tested in the synthesis of “trans”‐A2B2 porphyrins and A2B corroles. Furthermore, the dipyrromethanes – after oxidation to the dipyrromethenes – were found to be suitable ligands for metal ions giving access to functionalized ruthenium(II) metal complexes.

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Optimizing Photosensitizers with Type I and Type II ROS Generation Through Modulating Triplet Lifetime and Intersystem Crossing Efficiency

Yue,

Li,

Wang

et al. 2024

Adv Funct Materials

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Organic photosensitizers (PSs) can generate reactive oxygen species (ROS) via electron transfer (type I) and energy transfer (type II) pathways during photodynamic therapy (PDT). However, although numerous organic PSs have been constructed, the methods to optimize both type I and type II ROS generation are still not well explored. In this work, molecular engineering is applied to design three new organic PSs with varying triplet lifetimes and intersystem crossing (ISC) efficiency to achieve highly efficient type I&II ROS generation. The results reveal that after coated into nanoparticles (NPs) with DSPE‐PEG2000‐Biotin, the PS of mBDP‐PyH with the longest triplet lifetime and moderate ISC efficiency possesses good type II ROS and moderate type I ROS generation. With other properties being similar, the PS of mBDP‐2Py exhibits a shorter triplet lifetime, accompanied by concurrently reduced ROS generation for both types inside NPs. In contrast, the most potent PS of mBDP‐PyBr exhibits the shortest triplet lifetime but highly efficient ISC, with its NPs showing superior type I&II ROS generation. Moreover, both in vitro and in vivo experiments indicate that mBDP‐PyBr NPs display outstanding light toxicity under normoxic and hypoxic conditions. Overall, this study provides valuable guidance in designing effective organic PSs for PDT.

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Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro

Cited by 285 publications

References 26 publications

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

Synthesis of Porphyrinoids, BODIPYs, and (Dipyrrinato)ruthenium(II) Complexes from Prefunctionalized Dipyrromethanes

Optimizing Photosensitizers with Type I and Type II ROS Generation Through Modulating Triplet Lifetime and Intersystem Crossing Efficiency

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