Mikhail A. Filatov

Effects of Structural Deformations on Optical Properties of Tetrabenzoporphyrins: Free-Bases and Pd Complexes

A recently developed method of synthesis of pi-extended porphyrins made it possible to prepare a series of tetrabenzoporphyrins (TBP) with different numbers of meso-aryl substituents. The photophysical parameters of free-bases and Pd complexes of meso-unsubstituted TBPs, 5,15-diaryl-TBPs (Ar2TBPs) and 5,10,15,20-tetraaryl-TBPs (Ar4TBPs) were measured. For comparison, similarly meso-arylsubstituted porphyrins fused with nonaromatic cyclohexeno-rings, i.e. Ar(n)-tetracyclohexenoporphyrins (Ar(n)TCHPs, n = 0, 2, 4), were also synthesized and studied. Structural information was obtained by ab initio (DFT) calculations and X-ray crystallography. It was found that: 1) Free-base Ar4TBPs are strongly distorted out-of-plane (saddled), possess broadened, red-shifted spectra, short excited-state lifetimes and low fluorescence quantum yields (tau(fl) = 2-3 ns, phi(fl) = 0.02-0.03). These features are characteristic of other nonplanar free-base porphyrins, including Ar4TCHPs. 2) Ar2TBP free-bases possess completely planar geometries, although with significant in-plane deformations. These deformations have practically no effect on the singlet excited-state properties of Ar2TBPs as compared to planar meso-unsubstituted TBPs. Both types of porphyrins retain strong fluorescence (tau(fl) = 10-12 ns, phi(fl) = 0.3-0.4), and their radiative rate constants (k(r)) are 3-4 times higher than those of planar H2TCHPs. 3) Nonplanar deformations dramatically enhance nonradiative decay of triplet states of regular Pd porphyrins. For example, planar PdTCHP phosphoresces with high quantum yield (phi(phos) = 0.45, tau(phos) = 1118 micros), while saddled PdPh4TCHP is practically nonemissive. In contrast, both ruffled and saddled PdAr(n)TBPs retain strong phosphorescence at ambient temperatures (PdPh2TBP: tau(phos) = 496 micros, phi(phos) = 0.15; PdPh4TBP: tau(phos) = 258 micros, phi(phos) = 0.08). It appears that pi-extension is capable of counterbalancing deleterious effects of nonplanar deformations on triplet emissivity of Pd porphyrins.

π-Extended Dipyrrins Capable of Highly Fluorogenic Complexation with Metal Ions

The synthesis and properties of a new family of pi-extended dipyrrins capable of forming brightly fluorescent complexes with metal ions are reported. The metal complexes possess tunable spectral bands and exhibit different emission properties depending on the mode of metal coordination.

Triplet-Triplet Annihilation Upconversion Based Nanocapsules for Bioimaging Under Excitation by Red and Deep-Red Light

Non-toxic and biocompatible triplet-triplet annihilation upconversion based nanocapsules (size less than 225 nm) were successfully fabricated by the combination of miniemulsion and solvent evaporation techniques. A first type of nanocapsules displays an upconversion spectrum characterized by the maximum of emission at λmax = 550 nm under illumination by red light, λexc = 633 nm. The second type of nanocapsules fluoresces at λmax = 555 nm when excited with deep-red light, λexc = 708 nm. Conventional confocal laser scanning microscopy (CLSM) and flow cytometry were applied to determine uptake and toxicity of the nanocapsules for various (mesenchymal stem and HeLa) cells. Red light (λexc = 633 nm) with extremely low optical power (less than 0.3 μW) or deep-red light (λexc = 708 nm) was used in CLSM experiments to generate green upconversion fluorescence. The cell images obtained with upconversion excitation demonstrate order of magnitude better signal to background ratio than the cell images obtained with direct excitation of the same fluorescence marker.

Synthesis of 5,15-Diaryltetrabenzoporphyrins

A general method of synthesis of 5,15-diaryltetrabenzoporphyrins (Ar 2TBPs) has been developed, based on 2 + 2 condensation of dipyrromethanes followed by oxidative aromatization. Two pathways to Ar 2TBPs were investigated: the tetrahydroisoindole pathway and the dihydroisoindole pathway. In the tetrahydroisoindole pathway, precursor 5,15-diaryltetracyclohexenoporphyrins (5,15-Ar 2TCHPs) were assembled from cyclohexeno-fused meso-unsubstituted dipyrromethanes and aromatic aldehydes or, alternatively, by way of the classical MacDonald synthesis. In the first case, scrambling was observed. Aromatization by tetracyclone was more effective than aromatization by DDQ but failed in the cases of porphyrins with electron-withdrawing substituents in the meso-aryl rings. The dihydroisoindole pathway was found to be much superior to the tetrahydroisoindole pathway, and it was developed into a general preparative method, consisting of (1) the synthesis of 4,7-dihydroisoindole and its transformation into meso-unsubstituted dipyrromethanes, (2) the synthesis of 5,15-diaryloctahydrotetrabenzoporphyrins (5,15-Ar 2OHTBPs), and (3) their subsequent aromatization by DDQ. Ar 2TBP free bases exhibit optical absorption spectra similar to those of meso-unsubstituted tetrabenzoporphyrins and fluoresce with high quantum yields. Pd complex of Ph 2TBP was found to be highly phosphorescent at room temperature.

Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro

Heavy atom-free BODIPY-anthracene dyads (BADs) generate locally excited triplet states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with the anthracene moiety yielding highly fluorescent species. The steric demand of the alkyl substituents in the BODIPY subunit defines the site of 1O2 addition. Novel bis- and tetraepoxides and bicyclic acetal products, arising from rearrangements of anthracene endoperoxides were isolated and characterized. 1O2 generation by BADs in living cells enables visualization of the dyads distribution, promising new imaging applications.

The dihydroisoindole approach to linearly annelated π-extended porphyrins

The dihydroisoindole strategy for the synthesis of linearly annelated π-extended porphyrins is a common approach to tetrabenzo-, tetranaphtho-, and tetraanthraporphyrins with variable functionality and substitution patterns. This method implies the use of a common type of precursors involving the 4,7-dihydroisoindole moiety, which are the closest possible stable relatives of the unstable isoindole, benzoisoindole and naphthoisoindole. A key feature of this strategy is the unprecedented mildness of the final oxidative aromatization step, which accounts for synthetic versatility, better functional group tolerance and high purity of the products. Many new linearly annelated π-extended porphyrins of the tetrabenzo-, tetranaphtho-, and tetraanthraporphyrin families were produced and characterized for the first time, including soluble planar and highly emissive 5,15-diaryl derivatives. The double bond of the dihydroisoindole fragment can also be useful for further modification of the porphyrin by means of addition of cycloaddition reactions, leading to new, previously inaccessible porphyins bearing multiple halide, hydroxy, or acetoxy groups at the periphery.

Selective stepwise Suzuki cross-coupling reaction for the modelling of photosynthetic donor-acceptor systems.

A Suzuki reaction performed as a selective stepwise substitution of two boryl groups on a diarylporphyrin precursor is reported for straightforward construction of a porphyrin trimer, modeling photosynthetic donor-acceptor systems.

Tetraaryltetraanthra[2,3]porphyrins: Synthesis, Structure, and Optical Properties

A synthetic route to symmetrical tetraaryltetraanthra[2,3]porphyrins (Ar(4)TAPs) was developed. Ar(4)TAPs bearing various substituents in meso-phenyls and anthracene residues were prepared from the corresponding pyrrolic precursors. The synthesized porphyrins possess high solubility and exhibit remarkably strong absorption bands in the near-infrared region (790-950 nm). The scope of the method, selection of the peripheral substituents, choice of the metal, and their influence on the optical properties are discussed together with the first X-ray crystallographic data for anthraporphyrin.

Reversible oxygen addition on a triplet sensitizer molecule: protection from excited state depopulation†

We demonstrate that photoactivated oxygen addition to diphenylanthracene moities can be used as a tool for protection of porphyrins phosphorescence against oxygen quenching. Phosphorescent palladium(II) tetrabenzoporphyrin, covalently linked to four diphenylanthracene moieties, was synthesized and studied. Upon irradiation with ambient light or red laser in solution in air, addition of oxygen and formation of the corresponding endoperoxides were observed. Heating of the irradiated samples afforded the parent porphyrin material.

Bis- and trisporphyrin bio-inspired models for bacterial antennas and photosystems

This review presents the synthetic aspects and photophysical properties of trimeric systems constructed with a first unit consisting of a cofacial porphyrin and then of another porphyrin attached as a side arm. Two scenarios are dealt with. The first one is the case where the three chromophores are different, called donor 1–donor 2–acceptor, specifically where the cofacial fragment is composed of donor 1 and donor 2, and the side arm is the acceptor. They are considered as models for the apo-proteins used in the LH II (light harvesting device) in the purple photosynthetic bacteria. The second one is the case where the chromophores of the cofacial bisporphyrin residue are identical and are closely placed to each other for inter-ring π-interactions. The side arm is simply a mono-porphyrin, and therefore it is different. The cofacial bisporphyrin unit exhibits then similar characteristics to the special pairs located within the reaction center protein, and are designated as artificial special pairs. On the synthetic standpoint, the various pathways to access such models are presented fully exploiting the Suzuki methodology. On the photophysical side, a large emphasis will be placed on the singlet energy transfers. Cascade processes in the trimers donor 1–donor 2–acceptor are presented and each individual contributions donor 1 → donor 2; donor 2 → acceptor; donor → acceptor are addressed qualitatively and quantitatively. For the artificial special pairs flanked with an antenna, the effect of the spacer between the artificial special pair and the antenna will be discussed as well as the choice of substituents and metal demonstrating that one can reverse the orientation of the singlet energy transfer: artificial special pair → side arm or side arm → artificial special pair. Finally, the antenna effect are presented for one example of artificial special pair equipped with 6 semi-flexible dendritic antennas.