Porphyrin- and Bodipy-helicene conjugates: syntheses, separation of enantiomers and chiroptical properties.

The synthesis of several new compounds containing a chromophore and a helicenic moiety is reported. The preparation, characterisation and some physico-chemical studies are detailed. In particular, the two enantiomers of several chiral molecules of this type were separated by chiral HPLC (both analytically and in a preparative way) and their racemisation rates were determined for short-lived species. Electronic circular dichroism (ECD) and circular polarised luminescence (CPL) measurements were performed for the compounds with a very long racemisation half-life. Chiral porphyrins and Bodipys both gave ECD and CPL responses over a large area of the visible spectrum.

Remote Steric Control of the Tetrahedral Coordination Geometry around Heteroleptic Copper(I) Bis(Diimine) Complexes.

In this study, a series of new heteroleptic copper(I) bis(diimine) complexes are described. Using one highly hindered phenanthroline ligand and a second less-hindered diimine ligand led to unexpected results. Following a two-step one-pot method to obtain heteroleptic copper(I) complexes, an almost perfect tetrahedral coordination geometry around the copper(I) ion was obtained in several cases, despite the fact that at least one ligand was not sterically encumbered near the coordination site (at the position α to the nitrogen atoms of the ligand). This was demonstrated in the solid state by resolution of crystal structures, and these findings, corroborated by calculations, showed that the non-covalent interactions between the two diimine ligands present in these complexes were governing these structural features. The electronic properties of all complexes were also determined and the fluorescence lifetimes of two complexes were compared.

Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors.

A series of nickel(II) porphyrins bearing one or two bulky nitrogen donors at the meso positions were prepared by using Ullmann methodology or more classical Buchwald-Hartwig amination reactions to create the new C-N bonds. For several new compounds, single crystals were obtained, and the X-ray structures were solved. The electrochemical data of these compounds are reported. For a few representative examples, spectroelectrochemical measurements were used to clarify the electron exchange process. In addition, a detailed electron paramagnetic resonance (EPR) study was performed to estimate the extent of delocalization of the generated radical cations. In particular, electron nuclear double resonance spectroscopy (ENDOR) was used to determine the coupling constants. DFT calculations were conducted to corroborate the EPR spectroscopic data.

Porphyrins and Polyoxometalate Scaffolds.

Polyoxometalates (POMs) can act as unique reservoirs for multiple electron transfers. As POMs display only weak absorption in the visible spectrum, they can be associated with chromophores such as porphyrins and porphyrin antennae. In this Minireview, the research dedicated to the combination of porphyrins and polyoxometalates is put in context and the state of the art identifying the challenges addressed in the optimization of hybrid materials for applications is detailed.

Coordination-Driven Construction of Porphyrin Nanoribbons at a Highly Oriented Pyrolytic Graphite (HOPG)/Liquid Interface.

Nanostructures were built at the solid/liquid interface by self-assembly and/or coordination bonds. Metalloporphyrins bearing two external coordination sites and long alkyl chains allowed the self-assembly of the compounds on highly oriented pyrolitic graphite. After addition of a metal ion, long transition-metal linked porphyrin nanoribbons were obtained and visualized by scanning tunneling microscopy. In these porphyrin ribbons electronic delocalization is possible through the d orbitals of the connecting metal ions.

Peripherally Metalated Porphyrins with Applications in Catalysis, Molecular Electronics and Biomedicine.

Porphyrins are conjugated, stable chromophores with a central core that binds a variety of metal ions and an easily functionalized peripheral framework. By combining the catalytic, electronic or cytotoxic properties of selected transition metal complexes with the binding and electronic properties of porphyrins, enhanced characteristics of the ensemble are generated. This review article focuses on porphyrins bearing one or more peripheral transition metal complexes and discusses their potential applications in catalysis or biomedicine. Modulation of the electronic properties and intramolecular communication through coordination bond linkages in bis-porphyrin scaffolds is also presented.

Ring-Oxidized Zinc(II) Phthalocyanine Cations: Structure, Spectroscopy, and Decomposition Behavior.

A bromonium oxidizing agent was used to produce a ring-oxidized zinc phthalocyanine (PcZn), [PcZn(solvent)]•2[BArF4]2 (1·solvent), in good yield. This material is dimeric in the solid state with one axially coordinated solvent [tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME)] and close intradimer ring-ring distances of 3.18 and 3.136 Å (THF and DME respectively); this proximity facilitates strong antiferromagnetic coupling to yield diamagnetic dimers. 1·THF is present in solution as a monomer and a dimer. In CH2Cl2, the dimer is favored above 0.1 mM, and it is almost exclusively present in solvents with a high dielectric constant such as acetonitrile. The material 1·THF/DME decomposes in DME to a meso-nitrogen-protonated species, [HPcZn(DME)2][BArF4] (2), which was isolated and represents the first example of such a structurally characterized, protonated, unsubstituted PcM complex. A partially oxidized dimer or "pimer" [(PcZn(DME))2]•[BArF4] (3) was also structurally characterized and has a intradimer ring-ring distance of 3.192 Å, similar to 1·THF/DME. Dimer 3 also represents the first isolated PcM-based pimer. Electron paramagnetic resonance analysis of a 1.0 mM solution of 1·DME in DME showed the production of 3 over hours by the combination of 1·DME and 2 in solution.

Synthesis and Study at a Solid/Liquid Interface of Porphyrin Dimers Linked by Metal Ions.

Several porphyrin dimers linked by metal ions were prepared. One trimeric compound was also isolated and one porphyrin dimer linked by palladium(II) could be structurally characterized. In solution, the size of the new compounds was estimated by DOSY NMR techniques. These compounds all contained long aliphatic chains (O-C12H25), which were used to assemble them at a highly oriented pyrolytic graphite (HOPG)/liquid interface. The highly ordered arrays were visualized by scanning tunneling microscopy (STM).

Metal Linkage Effects on Ultrafast Energy Transfer.

We report the preparation of several new porphyrin homodimers bridged by a platinum(II) ion in which very intense electronic communication through the coordination link occurs. Moreover, the synthesis of a new porphyrin dyad and its photophysical properties are reported. This dyad exhibits the fastest singlet energy transfer ever reported for synthetic systems between a zinc(II) porphyrin and a porphyrin free base. This extremely fast transfer (∼100 femtoseconds) is in the same range as the fastest one measured in natural systems. This feature is due to the platinum(II) linker, which allows for strong MO couplings between the two porphyrin units as experimentally supported by electrochemistry and corroborated by DFT computations.

Ultrafast Singlet Energy Transfer in Porphyrin Dyads.

A weakly fluorescent Pt-bridged dyad composed of zinc(II) porphyrin (Zn; donor) and free base (Fb; acceptor) has been designed and exhibits an ultrafast singlet energy transfer between porphyrins. The use of larger atoms within the central linker significantly increases the MO coupling between the two chromophores and inherently the electronic communication.

Unexpected drastic decrease in the excited-state electronic communication between porphyrin chromophores covalently linked by a palladium(II) bridge.

A dyad built up of a zinc(II) porphyrin and the corresponding free base, [Zn-Fb], fused to N-heterocyclic carbene (NHCs) ligands, respectively acting as singlet energy donor and acceptor, and a bridging trans-PdI2 unit, along with the corresponding [Zn-Zn] and [Fb-Fb] dimers were prepared and investigated by absorption and emission spectroscopy and density functional computations. Despite favorable structural and spectroscopic parameters, unexpectedly slow singlet energy transfer rates are measured in comparison with the predicted values by the Förster theory and those observed for other structurally related dyads. This observation is rationalized by the lack of large molecular orbital (MO) overlaps between the frontier MOs of the donor and acceptor, thus preventing a double electron exchange through the trans-PdI2 bridge, and by an electronic shielding induced by the presence of this same linker preventing the two chromophores to fully interact via their transition dipoles.

Keto-enol equilibrium: stable tautomers of ortho-, meta-, and para-hydroquinones in large aromatics.

The synthesis of [6]helicene para-quinone starting from the 1,4-dimethoxy-[6]helicene derivative is presented. The demethylation reaction with boron tribromide led to unexpected results. Instead of the expected para-hydroquinone, the diketone tautomeric form was isolated. In contrast to the 1,4-hydroquinone and 1,4-dihydroxynaphthalene, the stable tautomers for the [4] and [6]helicenes were the aromatic diketones. These experimental results were corroborated by calculations. Additional calculations showed that these tautomeric species were indeed the stable forms of 1,4 and 1,3-hydroquinones when present in larger aromatics, in drastic contrast with 1,2-dihydroxy-aromatics (known as catechol).

Ground and excited state properties of new porphyrin based dyads: a combined theoretical and experimental study.

The properties of the ground and excited states of several porphyrins appended with external chelates coordinated to ruthenium-bisbipyridine units are reported. The important modification of the absorption spectrum upon coordination with the ruthenium complex showed that a significant electronic communication between the two subunits was present in the ground state. Experimental results were compared with quantum chemistry calculations performed at density functional theory and time-dependent density functional theory level. The influence of the exchange-correlation functional on the quality of the computed absorption spectrum is shown, and the better behavior of hybrid functionals over long-range corrected ones was rationalized. The excited states topology analysis, performed using natural transition orbitals, gave a more evident confirmation of the communication between the subunits and showed that these new compounds can be promising as dyes in dye-sensitized solar cells.

Synthesis of a helicene-fused porphyrin leading to a π-extended chiral chromophore.

The preparation of several covalently linked [6]-helicene-porphyrins is reported. A fused [6]-helicene-porphyrin π-extended aromatic system was isolated, the enantiomers separated and the chiroptical properties determined. The oxidative cyclodehydrogenation proved to be very effective for six-membered fused helical systems, but not suited for the formation of five-membered fused systems.

Locked pi-expanded chlorins in two steps from simple tetraarylporphyrins.

[reaction: see text] Upon tandem Reformatsky reaction, easily accessible porphyrinic ketones give "locked" chlorinic diester. Both ketones and diesters, as bases or palladium complexes, efficiently generate singlet dioxygen, as demonstrated by trapping with cholesterol.

Colorful Friedel-Crafts chemistry of meso-tetraarylporphyrins. An unexpected route to porphyrinic spiro dimers.

Under Friedel-Crafts conditions, meso-tetraarylporphyrins give porphyrin spiro dimers in good yield. This reaction involves acylation, acid-catalyzed cyclization, and dimerization. A stable dimer possessing three additional six-membered rings could be isolated and its structure determined. By modifying the substrate and reagents, intermediates could be isolated and characterized. The reactivity of the substrates, the side-reactions, and the concentration requirements to form the dimers, all explain why this reaction remained apparently unexplored in the widely used meso-tetraarylporphyrin series. [reaction: see text]

Porphyrin ring contraction: a one-pot reaction leading to divalent corroles.

Reaction of nickel meso-tetraarylporphyrins with benzoic anhydride and tin tetrachloride, followed by air oxidation under basic conditions, results in ring contraction, yielding divalent corroles.

Ultrafast energy transfer in a Pd(II)-bridged bisporphyrin dyad.

A free base porphyrin/zinc(II)porphyrin dyad bridged by a Pd(II) unit exhibits an ultrafast S1 energy transfer (1.5 × 10(12) s(-1)) due to significant MO couplings between the acceptor and the donor and a non-nil atomic contribution of the Pd-atom in the frontier MOs, hence ensuring π-conjugation.

Inexpensive and efficient Ullmann methodology to prepare donor-substituted porphyrins.

The preparation of porphyrins functionalized with one or two carbazoles (or phenoxazines) is described. The electron donors were introduced into one or two porphyrin meso positions by using the inexpensive Ullmann coupling procedure. Very good yields were obtained, and for two new compounds, the X-ray structures were solved. Preliminary electrochemical data coupled with electronic spectroscopy are also reported.