Preparation of BODIPY- fullerene and monostyryl BODIPY-fullerene dyads as heavy atom free singlet oxygen generators

Ünlü, Hasan; Okutan, Elif

doi:10.1016/j.dyepig.2017.03.055

Cited by 29 publications

(21 citation statements)

References 37 publications

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“…20,23 Regarding the chromophores used both as light-harvester and electron donor, 4,4'-Difluoro-4-bora-3a,4a-diaza-s-indacenes (referred to as BODIPYs) have recently gained more attention in the design of donor-C60 conjugates. [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] Indeed, BODIPYs (BDPs) are chemically stable and display remarkable photophysical properties, including high absorption coefficients and emission quantum yields. Another remarkable feature relies on the ease of functionalization of the BDP core, allowing to tune its spectral and electrochemical properties.…”

Section: Introductionmentioning

confidence: 99%

“…Another important feature relies on the ease of functionalization of the BODIPY core, allowing to tune its spectral and electrochemical properties. (41) In many examples, it has been shown that the PET in these BODIPY-C60 assemblies was the main pathway leading to charge-separated states, (26,27,29,(31)(32)(33)(34)(35)(36)(37)39) whereas energy transfer appeared as a competitive process in a few cases. (25,28) The occurrence of this PET in these BODIPY-fullerene systems observed in solution could also be exploited in the construction of photocurrent-generating photoelectrochemical cells.…”

Section: Introductionmentioning

confidence: 99%

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Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C₆₀ Dyad

et al. 2020

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A new donor–acceptor dyad composed of a BODIPY (4,4′-difluoro-4-bora-3a,4a-diaza-s-indacene) donor and a fullerene C60 acceptor has been synthesized and characterized. This derivative has been prepared using a clickable fullerene building block that bears an alkyne moiety and a maleimide unit. The post-functionalization of the maleimide group by a BODIPY thiol leads to a BODIPY-C60 dyad, leaving the alkyne moiety for further functional arrangement. On the basis of the combination of semi-empirical and density functional theory (DFT) calculations, spectroelectrochemical experiments, and steady-state and time-resolved spectroscopies, the photophysical properties of this new BODIPY-C60 dyad were thoroughly studied. By using semi-empirical calculations, the equilibrium of three conformations of the BODIPY-C60 dyad has been deduced, and their molecular orbital structures have been analyzed using DFT calculations. Two short fluorescence lifetimes were attributed to two extended conformers displaying variable donor–acceptor distances (17.5 and 20.0 Å). Additionally, the driving force for photoinduced electron transfer from the singlet excited state of BODIPY to the C60 moiety was calculated using redox potentials determined with electrochemical studies. Spectroelectrochemical measurements were also carried out to investigate the absorption profiles of radicals in the BODIPY-C60 dyad in order to assign the transient species in pump–probe experiments. Under selective photoexcitation of the BODIPY moiety, occurrences of both energy and electron transfers were demonstrated for the dyad by femtosecond and nanosecond transient absorption spectroscopies. Photoinduced electron transfer occurs in the folded conformer, while energy transfer is observed in extended conformers.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C₆₀ Dyad

et al. 2020

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“…The triplet excited states are responsive to diverse processes for deactivation, such as ground-state quenching, triplet-triplet annihilation via molecular oxygen leading to 1 O 2 , and electron transfer to donor molecules [17]. The longlived triplet states due to the ISC process of excited singlet states gave rise to a substantial interest for their prosperous applications, such as singlet oxygen generation for [22][23][24][25][26], enhancing photoinduced electric conductivity via formation of charge-separated state caused by the excited triplet state of fullerene [27][28][29] and in the applications of photovoltaics, photocatalysis, photoinduced charge separation, and molecular probes ( Figure 2) [30][31][32][33][34][35][36].…”

Section: Optical Studies Of Fullerenementioning

confidence: 99%

“…The previously reported triplet photosensitizers are usually transition-metal complexes, such as PtII/PdII porphyrin complexes, IrIII/RuII complexes, or heavy-atom derivatives of organic fluorophores since ISC is facilitated by the heavy atom spin-orbital coupling effect [91][92][93]. Designing these systems via chemical derivatization of a known heavy atom-free organic triplet photosensitizer is not a decisive way to prepare new organic triplet photosensitizers because even simple derivatization of the chromophore may diminishISC [25,26].Heavyatom-freeorganictriplet photosensitizers with absorption in visible range are highly desired and remained rare for TTA upconversion system (Figure 4) [36,87,94]. An intramolecular spin converter is used to overcome the aforementioned challenges.…”

Section: Optical Studies Of Fullerenementioning

confidence: 99%

“…In organic synthesis, oxidation is one of the primary reactions; thus, there has been an extensive research interest devoted on the use of singlet oxygen as photocatalysis in photooxidation reactions [25,26,107,108]. Huang et al used energy funneling for the first time with C 60 -BODIPY triads and tetrads as dual functional photocatalysis for two different photocatalytic reactions.…”

Section: Optical Studies Of Fullerenementioning

confidence: 99%

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Fullerene as Spin Converter

Okutan¹

2018

Fullerenes and Relative Materials - Properties and Applications

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It has now been more than 30 years since buckminsterfullerene became a real thing. An exclusive field of study called fullerene chemistry arises and is discovered to be unique in many respects. In a very short time, a great deal of effort has been devoted on the fullerene chemistry and properties of fullerene derivatives. The fields of fullerene and light-induced processes considerably overlapped, and now numerous wonderful examples are on exhibition. The large number of these systems has been designed to take advantage of the electron-accepting property of fullerene and broadcasts the fullerenes as universal spin converter advertising its perfect intersystem crossing (ISC) quantum yield where a spin converter can be identified as a chromophore that undergoes efficient ISC with a low first excited state (S 1 ), but does not necessarily strongly harvest visible light. Thus, donoracceptor systems in the field of light-induced processes within multicomponent fullerene arrays have been proposed as models for optical limiters, owing to the singlet oxygen production efficiency of C 60 and the C 60 derivatives in the field of medicinal chemistry.

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BOPHY‐Fullerene C₆₀ Dyad as a Photosensitizer for Antimicrobial Photodynamic Therapy

Lopez

Sarotti

Martínez

et al. 2021

Chemistry A European J

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A novel BOPHY–fullerene C60 dyad (BP‐C60) was designed as a heavy‐atom‐free photosensitizer (PS) with potential uses in photodynamic treatment and reactive oxygen species (ROS)‐mediated applications. BP‐C60 consists of a BOPHY fluorophore covalently attached to a C60 moiety through a pyrrolidine ring. The BOPHY core works as a visible‐light‐harvesting antenna, while the fullerene C60 subunit elicits the photodynamic action. This fluorophore–fullerene cycloadduct, obtained by a straightforward synthetic route, was fully characterized and compared with its individual counterparts. The restricted rotation around the single bond connecting the BOPHY and pyrrolidine moieties led to the formation of two atropisomers. Spectroscopic, electrochemical, and computational studies disclose an efficient photoinduced energy/electron transfer process from BOPHY to fullerene C60. Photodynamic studies indicate that BP‐C60 produces ROS by both photomechanisms (type I and type II). Moreover, the dyad exhibits higher ROS production efficiency than its individual constitutional components. Preliminary screening of photodynamic inactivation on bacteria models (Staphylococcus aureus and Escherichia coli) demonstrated the ability of this dyad to be used as a heavy‐atom‐free PS. To the best of our knowledge, this is the first time that not only a BOPHY–fullerene C60 dyad is reported, but also that a BOPHY derivative is applied to photoinactivate microorganisms. This study lays the foundations for the development of new BOPHY‐based PSs with plausible applications in the medical field.

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Preparation of BODIPY- fullerene and monostyryl BODIPY-fullerene dyads as heavy atom free singlet oxygen generators

Cited by 29 publications

References 37 publications

Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C₆₀ Dyad

Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C₆₀ Dyad

Fullerene as Spin Converter

BOPHY‐Fullerene C₆₀ Dyad as a Photosensitizer for Antimicrobial Photodynamic Therapy

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Preparation of BODIPY- fullerene and monostyryl BODIPY-fullerene dyads as heavy atom free singlet oxygen generators

Cited by 29 publications

References 37 publications

Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C60 Dyad

Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C60 Dyad

Fullerene as Spin Converter

BOPHY‐Fullerene C60 Dyad as a Photosensitizer for Antimicrobial Photodynamic Therapy

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Product

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Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C₆₀ Dyad

Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C₆₀ Dyad

BOPHY‐Fullerene C₆₀ Dyad as a Photosensitizer for Antimicrobial Photodynamic Therapy