Quantitative Structure‐Property Relationship Modelling for the Prediction of Singlet Oxygen Generation by Heavy‐Atom‐Free BODIPY Photosensitizers**

Buglak, Andrey A.; Charisiadis, Asterios; Sheehan, Aimee; Kingsbury, Christopher J.; Senge, Ma­thias O.; Filatov, Mikhail A.

doi:10.1002/chem.202100922

Cited by 34 publications

(26 citation statements)

References 126 publications

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“…The singlet oxygen quantification is an excellent tool to probe the triplet manifold of chromophoric systems . Highly reactive and prevalent singlet oxygen finds application in photodynamic therapeutic purposes since it kills the tumorous or diseased cells. , During the singlet oxygen quantification analysis, the triplet excitation energy of Se-PBI ( 3* Se-PBI ; photosensitizer) is transferred to ground-state (triplet) oxygen ( 3 Σ g ), resulting in singlet oxygen ( 1 Δ g ) generation. The singlet oxygen quantum yield, = 73.8% for Se-PBI, is one of the remarkable values reported among the modified PBI derivatives (Table S2 and Figure S13).…”

Section: Resultsmentioning

confidence: 99%

“…The 1 O 2 quantum yields ( ) of the photosensitizers were calculated with Rose Bengal (RB) as a standard ( = 0.80 in methanol). , The absorbance of the 1 O 2 scavenger 1,3-diphenylisobenzofuran (DPBF) was adjusted to be around 1.0 in aerated dimethylformamide (DMF). Then, a photosensitizer ( Se-PBI ) was added to the cuvette, and the absorbance of the photosensitizer was adjusted to be around 0.2–0.3.…”

Section: Methodsmentioning

confidence: 99%

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Ultrafast Intersystem Crossing in Selenium-Annulated Perylene Bisimide

et al. 2022

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An intersystem crossing (ISC), the non-radiative transition between two electronic states with different spin multiplicities, is ubiquitous and imperative in molecular photochemistry. The manifestation of a triplet manifold in π-conjugated chromophoric materials has a crucial role in enhancing the efficiency of photofunctional devices. Herein, we explore the triplet-state population in a series of chalcogen-annulated perylene bisimides (O-PBI, S-PBI, and Se-PBI), where the selenium-annulated PBI (Se-PBI) exhibits a near-quantitative triplet quantum yield ( = 94 ± 1%). Annulation of Se in the PBI core results in a drastic decrease in the fluorescence quantum yield ( = 1.5 ± 0.2%) compared to the bare PBI ( = 97.0 ± 1%), indicating the possibility of an efficient non-radiative decay pathway in the Se-PBI motif. Femtosecond and nanosecond transient absorption measurements unambiguously confirmed the ultrafast triplet population in Se-PBI with an ISC rate constant of = 2.39 × 1010 s–1 and the triplet-state decay to the ground state with a time constant of 3.78 μs. A theoretically calculated spin–orbit coupling constant (V SOC) of 122.4 cm–1 employing the SA-CASSCF/NEVPT2 method has rationalized the excited-state dynamics of Se-PBI. By virtue of the poor SOC between the singlet and triplet states, we observed a partial triplet population in S-PBI, whereas ISC is negligible in O-PBI. We demonstrate an increase in the spin–orbit coupling constant ( ≪ < ) and rate constant of ISC ( ≪ < ) across the series of chalcogen-annulated PBIs (O-PBI, S-PBI, and Se-PBI). The heavier chalcogenide PBI (Se-PBI) thus adds to the array of potential organic photoactive materials for the design of efficient solar energy conversion devices.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Ultrafast Intersystem Crossing in Selenium-Annulated Perylene Bisimide

et al. 2022

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“…36 Although predicting the efficiency of SOCT for a given structure in different media is still challenging, recently, we performed the first quantitative structure-property relationship (QSPR) study of these systems and developed a method for predicting singlet oxygen generation quantum yields for heavyatom-free BODIPYs in different solvents based on a combination of quantum mechanical molecular descriptors and topological descriptors. 37 QSPR analysis showed that structures containing a higher number of electron donor/acceptor subunits, e.g., donor-acceptor-donor (D-A-D) and acceptor-donor-acceptor triads, in general exhibit less pronounced solvent dependence of triplet state formation compared to D-A dyads. Such triads have been actively studied as materials for photovoltaics 38 and it has been demonstrated that intramolecular charge transfer (ICT) in these systems is faster than in D-A dyads.…”

Section: Introductionmentioning

confidence: 99%

Charge transfer mediated triplet excited state formation in donor–acceptor–donor BODIPY: Application for recording of holographic structures in photopolymerizable glass

et al. 2022

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“…Except for BODIPYs, it is therefore still unclear whether these complexes have any potential as photosensitizers for PDT. An example of a new research direction is investigating the possibility of enhancement triplet generation in AlDIPYs and other p-block mono(dipyrrinato) complexes by using similar techniques as developed for BODIPY's such as structural modifications [232]. Due to their similarity, tuning the photophysical properties tris(dipyrrinato) complexes with Ga(III) and In(III) metal ions is expected to be possible in an identical way as has been done for bis(dipyrrinato)Zn(II) complexes.…”

Section: Future Prospectsmentioning

confidence: 99%

Metal Coordination Effects on the Photophysics of Dipyrrinato Photosensitizers

Teeuwen¹,

Melissari²,

Senge³

et al. 2022

Preprint

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Within this work we review the metal coordination effect on the photophysics of metal dipyrrinato complexes. Dipyrrinato complexes are promising candidates in the search for alternative transition metal photosensitizers for application in photodynamic therapy (PDT). These complexes can be activated by irradiation with light of a specific wavelength, after which cytotoxic reactive oxygen species (ROS) are generated. The metal coordination allows for the use of the heavy atom effect, which can enhance the triplet generation necessary for generation of ROS. Additionally, the flexibility of these complexes for metal ions, substitutions and ligands allows the possibility to tune their photophysical properties. A general overview of the mechanism of photodynamic therapy and the properties of the triplet photosensitizers is given, followed by further details of dipyrrinato complexes described in the literature that show relevance as photosensitizers for PDT. In particular, the photophysical properties of Re(I), Ru(II), Ir(III), Ni(II), Cu(II), Pd(II), Pt(II), Zn(II), Ga(III), In(III), Al(III), Sn(II), and P dipyrrinato complexes are discussed. The potential for future development in the field of (dipyrrinato)metal complexes is addressed and several new research topics are suggested throughout this work. We propose that significant advances could be made for heteroleptic bis(dipyrrinato)zinc(II) and homoleptic bis(dipyrrinato)palladium(II) complexes and their application as photosensitizers for PDT.

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Quantitative Structure‐Property Relationship Modelling for the Prediction of Singlet Oxygen Generation by Heavy‐Atom‐Free BODIPY Photosensitizers**

Abstract: Supporting information for this article is given via a link at the end of the document.

Cited by 34 publications

References 126 publications

Ultrafast Intersystem Crossing in Selenium-Annulated Perylene Bisimide

Ultrafast Intersystem Crossing in Selenium-Annulated Perylene Bisimide

Charge transfer mediated triplet excited state formation in donor–acceptor–donor BODIPY: Application for recording of holographic structures in photopolymerizable glass

Metal Coordination Effects on the Photophysics of Dipyrrinato Photosensitizers

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