New Conjugated <i>meso</i>‐Tetrafluorenylporphyrin‐Cored Derivatives as Fluorescent Two‐Photon Photosensitizers for Singlet Oxygen Generation

Yao, Dandan; Zhang, Xu; Triadon, Amédée; Richy, Nicolas; Mongin, Olivier; Blanchard‐Desce, Mireille; Paul, Frédéric; Paul-Roth, Christine O.

doi:10.1002/chem.201604654

Cited by 24 publications

(53 citation statements)

References 75 publications

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“…For these dendrimers, the 2,7-fluorenyl arms were connected directly to the meso positions of the central porphyrin core (i.e., featuring TFP core). Interestingly, in these assemblies, the conjugated peripheral arms incorporate fluorene units at both terminal and internal positions [26]. We also observed that the various fluorene-containing dendrons act as light-harvesting antennae, before transferring their energy to the central porphyrin core.…”

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confidence: 66%

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confidence: 70%

“…We also observed that the various fluorene-containing dendrons act as light-harvesting antennae, before transferring their energy to the central porphyrin core. Although the emission quantum yields are slightly diminished compared to that for the smaller TFP reference compound [20], we showed that their brightness was much improved [26].Following our initial goal to further improve the luminescence quantum yield of the photosensitizers with flexible arms [22,23,25], we now wondered about the impact of replacing the porphyrin central core by a phthalocyanine ring. Based on literature reports, this tetrapyrrolic unit should be able to photosensitize oxygen with an efficiency similar to that of the meso-tetraarylporphyrin core once metalated by Zn(II) [27], but should also present a significantly improved fluorescence quantum yield [7].…”

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confidence: 96%

“…As a result, new oxygen photosensitizers with significantly improved brightness over H 2 TPP could be obtained by these means [25]. Furthermore, the presence of several fluorenyl units at the periphery of the central macrocycle also allowed for a significant increase in the two-photon absorption (2PA) cross-section maximum at lowest energy, another very desirable feature when targeting PDT or theranostic applications in the near-infrared (NIR) range [14,15].We can notice that, after having studied these non-conjugated TPP-based porphyrin dendrimers featuring flexible ether linkers (Figure 1), we considered more recently porphyrin dendrimers with conjugated peripheral arms [26]. Thus, a series of meso-substituted porphyrin dendrimers incorporating an increasing number of fluorenyl units, featuring fully conjugated alkynyl linkers, was studied.…”

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confidence: 99%

“…We can notice that, after having studied these non-conjugated TPP-based porphyrin dendrimers featuring flexible ether linkers (Figure 1), we considered more recently porphyrin dendrimers with conjugated peripheral arms [26]. Thus, a series of meso-substituted porphyrin dendrimers incorporating an increasing number of fluorenyl units, featuring fully conjugated alkynyl linkers, was studied.…”

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Phthalocyanine-Cored Fluorophores with Fluorene-Containing Peripheral Two-Photon Antennae as Photosensitizers for Singlet Oxygen Generation

et al. 2020

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A series of free base and Zn(II) phthalocyanines featuring fluorenyl antennae linked by methoxy or oxo bridges to the phthalocyanine core (Pc) were synthesized and characterized. Selected linear and nonlinear (two-photon absorption) optical properties of these new compounds were subsequently studied. As previously observed for related porphyrin dendrimers bearing 2-fluorenyl peripheral dendrons, an efficient energy transfer occurs from the peripheral antennae to the central phthalocyanine core following excitation in the fluorenyl-based π-π* absorption band of these chromophores. Once excited, these compounds relax to the ground state, mostly by emitting intense red light or by undergoing intersystem crossing. As a result, the tetrafunctionalized Zn(II) phthalocyanines are fluorescent, but can also efficiently photosensitize molecular oxygen in tetrahydrofurane (THF), forming singlet oxygen with nearly comparable yields to bare Zn(II) phthalocyanine (ZnPc). In comparison with the latter complex, the positive role of the fluorenyl-containing antennae on one-and two-photon brightness (2PA) is presently demonstrated when appended in peripheral (β) position to the phthalocyanine core. Furthermore, when compared to known porphyrin analogues, the interest in replacing the porphyrin by a phthalocyanine as the central core to obtain more fluorescent two-photon oxygen photosensitizers is clearly established. As such, this contribution paves the way for the future development of innovative biphotonic photosensitizers usable in theranostics.Molecules 2020, 25, 239 2 of 30 studying new porphyrin-or phthalocyanine-based molecular assemblies that might efficiently undergo two-photon excitation [10-13] while presenting a significant luminescence, constitutes an appealing goal for researchers interested in developing new photosensitizers for theranostic applications [4,5,[14][15][16]. Along these lines, some of us [17,18] and others [19], independently reported that fluorenyl units, when appended at the meso positions of porphyrins, were particularly suited to enhance the fluorescence quantum yields of this macrocyclic core, most likely by limiting the rate of non-radiative decay via internal conversion [20]. Thus, tetrafluorenylporphyrin (H 2 TFP) [21] features a quantum yield of 24% compared to that tetraphenylporphyrin (H 2 TPP; Φ F = 12%) taken as a reference compound (Figure 1) [18]. Subsequent photophysical studies with tetra(fluorenylmethoxyphenyl)porphyrin (H 2 TOFP), octa(fluorenylmethoxy)tetraphenylporphyrin (H 2 OOFP), or hexadeca(fluorenylmethoxy)tetra-phenylporphyrin (H 2 SOFP) featuring four, eight [22] and sixteen peripheral fluorenyl groups [23], respectively, evidenced that 2-fluorenyl units were also able to enhance the luminescence quantum yield of the central tetraphenylporphyrin (TPP) core when appended by methoxy bridges to the meso-phenyl rings of a central H 2 TPP core (Figure 1). In these molecular assemblies, the fluorene groups play the role of light-harvesting "antennae". Once photoexcited in their fi...

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confidence: 66%

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confidence: 70%

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confidence: 96%

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confidence: 99%

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confidence: 99%

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Phthalocyanine-Cored Fluorophores with Fluorene-Containing Peripheral Two-Photon Antennae as Photosensitizers for Singlet Oxygen Generation

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Dendrimeric Nanoparticles for Two‐Photon Photodynamic Therapy and Imaging: Synthesis, Photophysical Properties, Innocuousness in Daylight and Cytotoxicity under Two‐Photon Irradiation in the NIR

Sourdon

Gary‐Bobo

Maynadier

et al. 2019

Chemistry A European J

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The synthesis and the photophysical properties of a new class of fully organic monodisperse nanoparticles for combined two‐photon imaging and photodynamic therapy are described. The design of such nanoparticles is based on the covalent immobilization of a dedicated quadrupolar dye that combines excellent two‐photon absorbing (2PA) properties, fluorescence and singlet oxygen generation ability, in a phosphorous‐based dendrimeric architecture. First, a bifunctional quadrupolar dye bearing two different grafting moieties, a phenol function and an aldehyde function, was synthesized. It was then covalently grafted through its phenol function to a phosphorus‐based dendrimer scaffold of generation 1. The remaining aldehyde functions were then used to continue the dendrimer synthesis up to generation 2, introducing finally 24 water‐solubilizing triethyleneglycol chains at its periphery. A dendrimer confining 12 photoactive quadrupolar units in its inner scaffold and showing water solubility was thus obtained. Interestingly, the G1 and G2 dendrimers retain some fluorescence as well as significant singlet oxygen production efficiencies while they were found to show very high 2PA cross‐sections in a broad range of the NIR biological spectral window. Hydrophilic dendrimer G2 was tested in vitro on breast cancer cells, first in one‐ and two‐photon microscopy, which allowed for visualization of their cell internalization, then in two‐photon photodynamic therapy. While being nontoxic in the dark and, more importantly, under exposure to daylight, dendrimer G2 proved to be a very efficient cell‐death inducer only under two‐photon irradiation in the NIR.

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Giant Star‐shaped meso‐substituted Fluorescent Porphyrins with Fluorenyl‐containing Arms Designed for Two‐photon Oxygen Photosensitization

Shi,

Sun,

Richy

et al. 2024

Chemistry A European J

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In the continuation of previous studies on carbon‐rich meso‐tetraarylporphyrins featuring 2,7‐fluorene units at their periphery, the effect of changing the peripheral dendritic arms for linear arms on . their oxygen‐photosensitizing ability, their fluorescence and their two‐photon absorption (2PA) properties is now analyzed. Thus, starburst porphyrins possessing up to twenty conjugated fluorenyl units were isolated and studied. More precisely, a series of five new free‐base porphyrins featuring fully conjugated arms incorporating an increasing number of fluorenyl groups connected via 1,2‐alkenyl spacers were synthesized, along with their Zn(II) complexes. Upon excitation in the arm‐centred band, an efficient energy transfer takes place from the peripheral fluorenyl units to the central porphyrin core, leading to intense red‐light emission and oxygen photosensitization by the latter. More interestingly, while the linear optical properties of these porphyrins were only slightly improved compared to those of their dendrimer analogues for photodynamic therapy (PDT) or fluorescence imaging, their 2PA cross‐sections were much more significantly boosted, evidencing the key role played by different structures on nonlinear optical properties. Finally, by comparison with other porphyrin‐based two‐photon photosensitizers reported in the literature, we show that these new “semi‐disconnected” starburst systems exhibit a remarkable trade‐off between intrinsic 2PA, fluorescence and oxygen photosensitization.

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New Conjugated meso‐Tetrafluorenylporphyrin‐Cored Derivatives as Fluorescent Two‐Photon Photosensitizers for Singlet Oxygen Generation

Cited by 24 publications

References 75 publications

Phthalocyanine-Cored Fluorophores with Fluorene-Containing Peripheral Two-Photon Antennae as Photosensitizers for Singlet Oxygen Generation

Phthalocyanine-Cored Fluorophores with Fluorene-Containing Peripheral Two-Photon Antennae as Photosensitizers for Singlet Oxygen Generation

Dendrimeric Nanoparticles for Two‐Photon Photodynamic Therapy and Imaging: Synthesis, Photophysical Properties, Innocuousness in Daylight and Cytotoxicity under Two‐Photon Irradiation in the NIR

Giant Star‐shaped meso‐substituted Fluorescent Porphyrins with Fluorenyl‐containing Arms Designed for Two‐photon Oxygen Photosensitization

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