Régis Rein

Synthesis and Characterization of Novel Pyrene-Dendronized Porphyrins Exhibiting Efficient Fluorescence Resonance Energy Transfer: Optical and Photophysical Properties

A novel series of pyrene dendronized porphyrins bearing two and four pyrenyl groups (Py(2)-TMEG1 and Py(4)-TMEG2) were successfully synthesized. First and second generation Fréchet type dendrons (Py(2)-G1OH and Py(4)-G2OH) were prepared from 1-pyrenylbutanol and 3,5-dihydroxybenzyl alcohol. These compounds were further linked to a trimesitylphenylporphyrin containing a butyric acid spacer via an esterification reaction to obtain the desired products. Dendrons and dendronized porphyrins were fully characterized by FTIR and (1)H NMR spectroscopy and their molecular weights were determined by matrix-assisted laser desorption ionization time of flight mass spectrometry. Their optical and photophysical properties were studied by absorption and fluorescence spectroscopies. The formation of dynamic excimers was detected in the pyrene-labeled dendrons, with more excimer being produced in the higher generation dendron. The fluorescence spectra of the pyrene dendronized porphyrins exhibited a significant decrease in the amount of pyrene monomer and excimer emission, jointly with the appearance of a new emission band at 661 nm characteristic of porphyrin emission, an indication that fluorescence resonance energy transfer (FRET) occurred from one of the excited pyrene species to the porphyrin. The FRET efficiency was found to be almost quantitative ranging between 97% and 99% depending on the construct. Model Free analysis of the fluorescence decays acquired with the pyrene monomer, excimer, and porphyrin core established that only residual pyrene excimer formation in the dendrons could occur before FRET from the excited pyrene monomer to the ground-state porphyrin core.

Polypeptides with pendant porphyrins of defined sequence of chromophores: towards artificial photosynthetic systems

In this paper we now report our ongoing progress in the preparation of artificial photosynthetic systems through the preparation of light harvesting multi-porphyrins. A tetramer, constituted of a central dipeptide functionalized by two free-base porphyrins and surrounded by one amino-acid bearing a pendant Zn(II) porphyrin on each side, has been chosen. The optical and photophysical properties of this tetramer have been studied by absorption and fluorescence spectroscopy. In addition, the energy transfer phenomenon has been studied and monitored by femtosecond time-resolved fluorescence. Our results indicate that the excited state dynamics redounding in the excitation being localized in the inner free-base porphyrins takes place in the time scale of approximately 1 ps.

Adjustable cavity for host-guest recognition in cofacial bis-porphyrinic tweezer

The synthesis of a cofacial bis-porphyrinic tweezer bearing a tris-anthracenic spacer is reported. Its behavior as host has been evidenced as well as the ability of its cavity to adjust to guests of various sizes.

Structure-reactivity correlations in extended multi-porphyrinic architectures

In addition to controlling the structure of multi-chromophoric arrays, monitoring the spatial orientation of the chromophores in artificial light harvesting devices is a challenge of growing interest. We report in this article our recent advances in this field. It is expected that a better understanding of the physicochemical properties of rigid cofacial porphyrinic tweezers and an identification of the factors governing them will be crucial for the design and the elaboration of new nano-molecules endowed with original properties. Extended multi-porphyrinic architectures, polypeptides bearing pendant porphyrins have been synthesized as linear devices, and a star-like pentaporphyrin as an arborescent array. The structure and the original conformation of the latter confer to this system an unusual duality in its physicochemical properties.

Pre-organized dinucleosides with pendant porphyrins for the formation of sandwich type complexes with DABCO with high association constants

We report herein the synthesis of a dinucleotide bearing pendant porphyrins dedicated to adopt a pre-organized coformation with face-to-face porphyrins, and capable to self-organize in a stable sandwich type complexe with bidentate base such as DABCO. Earlier studies demonstrated that a peptidic linker does not provide sufficient pre-organization to enhance significantly the association constant with bidentate bases such as DABCO on the contrary of some other flexible linkers such as uridine or 2′-deoxyuridine. We document herein that the gain in stability for the formation of sandwich type host–guest complex with DABCO can be even greater when a dinucleotide linker is used. Such pre-organization increases the association constants by one to two orders of magnitude when compared to the association constants of the same bidentate ligands with a reference Zn(II) porphyrin. Comparison of these results with those obtained for rigid tweezers shows a better efficiency of the flexible nucleosidic dimers. We thus document the fact that the choice of rigid spacers is not the only way to pre-organize bis-porphyrins, and that some well-chosen nucleosidic linkers offer an interesting option for the synthesis of such devices. Furthermore, the chirality and enantio-purity of the nucleosidic linkers paves the way toward the selective complexation of enantio-pure bidentate guests and the resolution of racemates.

Light harvesting porphyrin-crown ether conjugates: toward artificial photosynthetic systems

In this paper we report on our ongoing progress in the preparation of artificial photosynthetic systems through the preparation of light harvesting multi-porphyrins. The synthesis of these antennae is described herein and the energy transfer capabilities of these devices demonstrated. A terminal porphyrin/crown ether conjugate has been maintained in each case to ensure a coordination site for the complexation of an ammonium/C60 derivative, which could be chosen as the electron acceptor partner for the preparation of artificial photosynthetic systems.

Cofacial tris-porphyrins with anthracenic spacer

In order to check if the parallel orientation of the chlorophylls in the light harvesting antennae of the photosynthetic system plays a key role in the efficiency of the energy transfer process, we synthesized three rigid tris-porphyrins bearing di-ethynyl-anthracenic spacers. The synthesis of this family of trimers in which porphyrins are held in a cofacial orientation by an anthracenic spacer is here described, as well as the NMR comparison between the different porphyrinic wires. This constitutes a first step toward the elaboration of more sophisticated light collecting devices. More specifically, these trimers, in which the porphyrins are held in a parallel conformation, constitute an approach toward the synthesis of rigid molecular wires.

Efficiency of Dinucleosides as the Backbone to Pre-Organize Multi-Porphyrins and Enhance Their Stability as Sandwich Type Complexes with DABCO

Flexible linkers such as uridine or 2′-deoxyuridine pre-organize bis-porphyrins in a face-to-face conformation, thus forming stable sandwich complexes with a bidentate base such as 1,4-diazabicyclo[2.2.2]octane (DABCO). Increased stability can be even greater when a dinucleotide linker is used. Such pre-organization increases the association constant by one to two orders of magnitude when compared to the association constant of DABCO with a reference porphyrin. Comparison with rigid tweezers shows a better efficiency of nucleosidic dimers. Thus, the choice of rigid spacers is not the only way to pre-organize bis-porphyrins, and well-chosen nucleosidic linkers offer an interesting option for the synthesis of such devices.