Rational Design of Advanced Photosensitizers Based on Orthogonal BODIPY Dimers to Finely Modulate Singlet Oxygen Generation

Epelde-Elezcano, Nerea; Palao, Eduardo; Manzano, Hegoi; Prieto‐Castañeda, Alejandro; Agarrabeitia, Antonia R.; Tabero, Andrea; Villanueva, Ángeles; Cerero, Santiago de la Moya; López‐Arbeloa, Íñigo; Martínez‐Martínez, Virginia; Ortiz, María J.

doi:10.1002/chem.201605822

Cited by 97 publications

(120 citation statements)

References 31 publications

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“…Ortiz et al. confirmed that the intrinsic intramolecular CT character of the orthogonal BODIPY dimers was related to 1 O 2 generation . We considered that BODIPY‐MeAP in 1,4‐dioxane would follow a similar decay process to these BODIPY derivatives.…”

Section: Resultsmentioning

confidence: 91%

Aggregation‐Induced Singlet Oxygen Generation: Functional Fluorophore and Anthrylphenylene Dyad Self‐Assemblies

Kim

Zhou

Tohnai

et al. 2017

Chemistry A European J

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The assembly of monomeric building blocks can manifest the display of new properties, including optical, mechanical, and electrochemical functionalities. In this study, we sought to develop a functional fluorophore self-assembly that can generate reactive oxygen species only when aggregated. With an anthrylphenylene (AP) group, negatively charged and neutral fluorescein units form non-fluorescent H-aggregates in aqueous solution because of the weak intermolecular interaction between the anthracene and fluorescein moieties. In stark contrast, a boron dipyrromethene (BODIPY) and AP dyad produces two-color-emissive aggregates through the formation of an intermolecular charge-transfer (CT) complex between the electron-rich anthracene and electron-deficient BODIPY moieties. Furthermore, to our surprise, the BODIPY and AP dyad aggregates generate singlet oxygen ( O ) and photocytotoxicity upon excitation, indicating that the BODIPY-anthracene CT state favors an intersystem crossing process. Based on X-ray crystallographic analysis, the lattice-like molecular packing between the BODIPY and AP moieties was determined to bring about the unprecedented aggregation-induced O generation (AISG).

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Section: Resultsmentioning

confidence: 91%

Aggregation‐Induced Singlet Oxygen Generation: Functional Fluorophore and Anthrylphenylene Dyad Self‐Assemblies

Kim

Zhou

Tohnai

et al. 2017

Chemistry A European J

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“…For example, phenanthrene‐fused BODIPYs show red fluorescence ( λ FL =600–700 nm) and large ϵ values at the 0–0 transition ( ϵ 0–0 ≈60 000–140 000 m −1 cm −1 ) . Moreover, BODIPY derivatives with absorption and emission bands in the near‐infrared (NIR) region are also promising for photodynamic therapy (PDT) and two‐photon absorption (TPA) properties . However, little attention has been paid to a systematic discussion of structural and photophysical control, as well as large TPA properties, in the NIR region with regard to π‐extended BODIPY derivatives.…”

Section: Introductionmentioning

confidence: 99%

Systematic Control of Structural and Photophysical Properties of π‐Extended Mono‐ and Bis‐BODIPY Derivatives

Ito

Sakai

Suzuki

et al. 2019

Chemistry A European J

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A series of π‐extended mono‐ and bis‐BODIPY (BODIPY=boron‐dipyrromethene) derivatives, namely, benzo[a]phenanthrene‐fused BODIPY (Phena‐Mono‐BDP), benzo[a]anthracene‐fused BODIPY (Ant‐Mono‐BDP), and dibenz[a,h]anthracene (DBA)‐bridged bis‐BODIPY (Ant‐Bis‐BDP), were designed and synthesized to examine their structural, electrochemical, and photophysical properties. Single‐crystal X‐ray crystallographic analyses demonstrated the planar configuration of Ant‐Mono‐BDP, in contrast to that of nonplanar Phena‐Mono‐BDP, whereas Ant‐Bis‐BDP has a DBA‐centered planar configuration and two terminal nonplanar units of BODIPYs. The oxidation and reduction potentials agree with the estimated energies obtained through DFT calculations. The localized HOMO and LUMO states suggested the intramolecular charge‐transfer characteristics in these BODIPY derivatives. The absorption spectra of these compounds extended up to the near‐IR region. Strong redshifted trends of fluorescence spectra were observed in Ant‐Bis‐BDP with increasing solvent polarity, as supported by the differences in dipole moments estimated from Lippert–Mataga plots. To evaluate the excited‐state dynamics of these molecules, the fluorescence quantum yield (ΦFL) of Ant‐Bis‐BDP dramatically increased in the range from 0.05 to 0.86, with decreasing solvent polarity. Finally, the efficient two‐photon absorption cross section of Ant‐Bis‐BDP (ca. 1200 GM at λ=1000 nm) was also obtained by considering the large π‐extended structure (acceptor–donor–acceptor type).

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“…Unsubstituted BODIPY, for example, shows fluorescence efficiency near unity (0.97±0.03) and a long fluorescence lifetime of 6.89 ns in methanol, which leaves it little space to form the T 1 state. The heavy atom effect with iodine or bromine substitution and dimerization are often used to make BODIPY efficient in T 1 formation . By covalently linking an aryl as an electron‐donor unit (benzene, naphthalene, anthracene, or pyrene) onto the meso position of the BDP (Scheme ), we could make BODIPY compounds generate the T 1 state and hence singlet oxygen efficiently.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Electron Transfer‐based Halogen‐free Photosensitizers: Covalent meso‐Aryl (Phenyl, Naphthyl, Anthryl, and Pyrenyl) as Electron Donors to Effectively Induce the Formation of the Excited Triplet State and Singlet Oxygen for BODIPY Compounds

Zhang

Feng

2017

Chemistry An Asian Journal

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Pristine BODIPY compounds have negligible efficiency to generate the excited triplet state and singlet oxygen. In this report, we show that attaching a good electron donor to the BODIPY core can lead to singlet oxygen formation with up to 58 % quantum efficiency. For this purpose, BODIPYs with meso-aryl groups (phenyl, naphthyl, anthryl, and pyrenyl) were synthesized and characterized. The fluorescence, excited triplet state, and singlet oxygen formation properties for these compounds were measured in various solvents by UV/Vis absorption, steady-state and time-resolved fluorescence methods, as well as laser flash photolysis technique. In particular, the presence of anthryl and pyrenyl showed substantial enhancement on the singlet oxygen formation ability of BODIPY with up to 58 % and 34 % quantum efficiency, respectively, owing to their stronger electron-donating ability. Upon the increase in singlet oxygen formation, the fluorescence quantum yield and lifetime values of the aryl-BODIPY showed a concomitant decrease. The increase in solvent polarity enhances the singlet oxygen generation but decreases the fluorescence quantum yield. The results are explained by the presence of intramolecular photoinduced electron transfer from the aryl moiety to BODIPY core. This method of promoting T formation is very different from the traditional heavy atom effect by I, Br, or transition metal atoms. This type of novel photosensitizers may find important applications in organic oxygenation reactions and photodynamic therapy of tumors.

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Rational Design of Advanced Photosensitizers Based on Orthogonal BODIPY Dimers to Finely Modulate Singlet Oxygen Generation

Cited by 97 publications

References 31 publications

Aggregation‐Induced Singlet Oxygen Generation: Functional Fluorophore and Anthrylphenylene Dyad Self‐Assemblies

Aggregation‐Induced Singlet Oxygen Generation: Functional Fluorophore and Anthrylphenylene Dyad Self‐Assemblies

Systematic Control of Structural and Photophysical Properties of π‐Extended Mono‐ and Bis‐BODIPY Derivatives

Photoinduced Electron Transfer‐based Halogen‐free Photosensitizers: Covalent meso‐Aryl (Phenyl, Naphthyl, Anthryl, and Pyrenyl) as Electron Donors to Effectively Induce the Formation of the Excited Triplet State and Singlet Oxygen for BODIPY Compounds

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