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

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.

Encapsulation of Hydrophobic Porphyrins into Biocompatible Nanoparticles: An Easy Way to Benefit of Their Two-Photon Phototherapeutic Effect without Hydrophilic Functionalization.

Star-shaped hydrophobic porphyrins, acting as powerful fluorescent two-photon photosensitizers for oxygen in organic solvents, can easily be loaded into PMLABe polymeric nanoparticles at various concentrations. In this contribution, the performance of these porphyrin-containing nanoparticles in terms of photodynamic therapy (PDT) is compared to those of the corresponding water-soluble porphyrin analogues when irradiated in MCF-7 cancer cells. While quite promising results are obtained for performing PDT with these nanoparticles, validating this approach as a mean for using more easily accessible and less expensive photosensitizers, from a synthetic perspective, we also show that their luminescence can still be used for bioimaging purposes in spite of their confinement in the nanoparticles, validating also the use of these nano-objects for theranostic purposes.

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

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.

Biocompatible conjugated fluorenylporphyrins for two-photon photodynamic therapy and fluorescence imaging.

The photophysical properties of a new series of fluorenyl porphyrins bearing water-solubilising oligoethyleneglycol chains are described. These biocompatible compounds present very good two-photon absorption and singlet oxygen generation properties, while retaining some fluorescence in water. After testing in vitro on breast cancer cells, some of them were shown to be efficient non-toxic two-photon photosensitisers allowing for fluorescence imaging, thus demonstrating their theranostic potential.

Fluorenylporphyrins functionalized by electrochromic ruthenium units as redox-triggered fluorescence switches.

Two dyads containing tris- and tetrakis-meso-fluorenyl-substituted porphyrin and ethynylruthenium units, 1 and 2, were investigated by emission spectro-electrochemical (SEC) methods for their potential use as fluorescence switches. The ruthenium group as a potential electron donor and the porphyrin as a potential electron acceptor are connected by a phenylene bridge in 1 and by a fluorenylene bridge in 2. The new fluorenyl-linked dyad 2 was probed by UV-visible, near-infrared (NIR) and infrared (IR) absorption SEC methods, and the properties interpreted with the aid of hybrid-DFT computations, for comparison with reported data for 1.

Synthesis, characterization and third-order nonlinear optical properties of a dodecaruthenium organometallic dendrimer with a zinc(ii) tetraphenylporphyrin core.

A new Zn(ii) porphyrin-based dendrimer (52) containing twelve Ru(ii) alkynyl fragments, has been prepared following a convergent approach in two steps from 5,10,15,20-tetra(4-ethynylphenyl)porphyrinatozinc(ii) (6). The cubic nonlinear optical (NLO) properties of 52 and other derivatives of 6 have been measured by third-harmonic generation (THG) at 1907 nm and by Z-scan over the spectral range 500-1700 nm, revealing the remarkable NLO response of 52 in the near-IR range. These results highlight the beneficial role of the extended "cross fourchée"-like polymetallic structure of 52 on its third-order NLO properties.

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

A series of three conjugated meso-porphyrin dendrimers containing conjugated dendrons featuring 2,7-fluorenyl groups, incorporating overall 8, 12, or 28 fluorenyl units have been synthesized and characterized. The photophysical properties of these new compounds were studied in the context of photodynamic therapy. The relevant linear and nonlinear optical properties were measured in organic media and useful structure-properties relationships were derived.

Synthesis and Characterization of New Conjugated Fluorenyl-Porphyrin Dendrimers for Optics.

A new family of conjugated meso-tetraphenylporphyrin-based dendrimers with four (TPP1, TPP2), eight (TPP3, TPP4, TPP5) and up to sixteen (TPP6) fluorenyl groups has been synthesized and fully characterized. These tetraphenylporphyrin-cored dendrimers present peripheral alkynyl π-conjugated dendrons with fluorenyl termini. The meso-aryl rings of these porphyrins are functionalized either in para- (TPP1, TPP2, and TPP3) or meta-positions (TPP4, TPP5, and TPP6).

New donor-acceptor conjugates based on a trifluorenylporphyrin linked to a redox-switchable ruthenium unit.

Reactions of the 16-electron ruthenium complex [Ru(dppe)2Cl][PF6] with metal-free and zinc ethynylphenyltrifluorenylporphyrins and respectively, gave the new dyads and with ethynylruthenium group as a potential electron donor and the porphyrin as a potential electron acceptor. The redox properties of the porphyrins were investigated by cyclic voltammetry and UV spectroelectrochemistry (SEC), which reveal that the monocation and monoanion of metal-free porphyrin are stable under these conditions whereas the formation of the corresponding radical cation or anion of the zinc porphyrin was accompanied by partial decomplexation of the zinc ion. Oxidations of the dyads and gave stable radical cations as probed using IR, NIR and UV SEC methods.

A hybrid ruthenium alkynyl/zinc porphyrin "Cross Fourchée" with large cubic NLO properties.

A new Zn(ii) porphyrin-cored ruthenium alkynyl dendrimer (2) containing twelve Ru(κ(2)-dppe)2 bis-alkynyl fragments has been prepared in two steps from 5,10,15,20-tetra(4-ethynylphenyl)porphyrinatozinc(ii) and shown to be highly active for third-harmonic generation (THG) at 1907 nm.