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With a direct band gap, superior charge carrier mobility, and uniformly distributed pores, graphdiyne (GDY) has stimulated tremendous interest from the scientific community. However, its broad application is greatly limited by the complicated multistep synthesis process including complex deprotection of hexakis-[(trimethylsilyl)ethynyl]benzene (HEB-TMS) and peeling of GDY from the substrates. Here, we describe a deprotection-free strategy to prepare GDY powder by directly using HEB-TMS as the monomer. When CuCl was used as the catalysts in DMF solvent, the yield of GDY powder reached ≈100 %. More interestingly, uniformly dispersed CuO nanoparticles with an average diameter of ≈2.9 nm were in situ formed on GDY after the reaction. The prepared CuO/GDY was demonstrated an excellent co-catalyst for photocatalytic hydrogen evolution, comparable to the state-of-art Pt co-catalyst. The deprotection-free approach will widen the use of GDY and facilitate its scaling up to industrial level., J.L. acknowledges funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodovska-Curie Grant Agreement No 101030637. J.L. acknowledges the public grant overseen by the French National Research Agency (ANR) as part of the “Investissements d'Avenir” program (Labex NanoSaclay, reference: ANR-10-LABX-0035) for his post-doc position. M.N.G. acknowledges the public grant overseen by the French National Research Agency (ANR) as part of the ERANET-ACT3 call program and the Paris Ile-de-France Region (DIM RESPORE-2021-27) for financial support. L.Z and L.-Z.W. are grateful for financial support from the Strategic Priority Research Program of the Chinese Academy of Science (XDB17000000), Key Research Program of Frontier Science of the Chinese Academy of Sciences (QYZDY-SSW-JSC029). ICN2 acknowledges funding from Generalitat de Catalunya 2017 SGR 327. ICN2 was supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706) and was funded by CERCA Programme/Generalitat de Catalunya.

International audience; Iron porphyrins are among the best molecular catalysts for the electrocatalytic CO$_2$ reduction reaction. Powering these catalysts with the help of photosensitizers comes along with a couple of unsolved challenges that need to be addressed with much vigor. We have designed an iron porphyrin catalyst decorated with urea functions (UrFe) acting as a multipoint hydrogen bonding scaffold towards the CO$_2$ substrate. We found a spectacular photocatalytic activity reaching unreported TONs and TOFs as high as 7270 and 3720 h$^{-1}$ , respectively. While the Fe$^0$ redox state has been widely accepted as the catalytically active species, we show here that the Fe(I) species is already involved in the CO$_2$ activation, which represents the rate-determining step in the photocatalytic cycle. The urea functions help to dock the CO$_2$ upon photocatalysis. DFT calculations bring support to our experimental findings that constitute a new paradigm in the catalytic reduction of CO$_2$

Photophysical studies on a BODIPY-fullerene-distyryl BODIPY triad (BDP-C

Iron porphyrins are among the best molecular catalysts for the electrocatalytic CO

International audience; The synthesis of a methanofullerene platform bearing on one side an alkyne and on the other a protected alkyne is reported. This clickable fullerene building block was functionalized by two distinct BODIPY azido derivatives using a 1 st CuAAC/alkyne deprotection /2 nd CuAAC, sequence, through either stepwise or one-pot processes in an efficient manner. The triad displays strong absorption from 300 to 700 nm. The strong fluorescence quenching observed for the two BODIPYs within the triad is probably due to photo-induced energy and/or electron transfer events.

Graphdiyne (GDY), which features a highly π-conjugated structure, direct bandgap, and high charge carrier mobility, presents the major requirements for photocatalysis. Up to now, all photocatalytic studies are performed without paying too much attention on the GDY bandgap (1.1 eV at the GW many-body theory level). Such a narrow bandgap is not suitable for the band alignment between GDY and other semiconductors, making it difficult to achieve efficient photogenerated charge carrier separation. Herein, for the first time, it is demonstrated that tuning the electronic bandgap of GDY via H-substitution (H-GDY) promotes interfacial charge separation and improves photocatalytic H evolution. The H-GDY exhibits an increased bandgap energy (≈2.5 eV) and exploitable conduction band minimum and valence band maximum edges. As a representative semiconductor, TiO is hybridized with both H-GDY and GDY to fabricate a heterojunction. Compared to the GDY/TiO, the H-GDY/TiO heterojunction leads to a remarkable enhancement of the photocatalytic H generation by 1.35 times under UV–visible illumination (6200 µmol h g) and four times under visible light (670 µmol h g). Such enhancement is attributed to the suitable band alignment between H-GDY and TiO, which efficiently promotes the photogenerated electron and hole separation, as supported by density functional theory calculations., The work in Mons was supported by the Belgian National Fund for Scientific Research (FRS-FNRS). Computational resources were provided by the Consortium des Équipements de Calcul Intensif (CÉCI) funded by F.R.S.-FNRS under Grant No. 2.5020.11. J.C. is an FNRS research director. ICN2 acknowledges funding from Generalitat de Catalunya 2017 SGR 327 and the Spanish MINECO project ENE2017-85087-C3. ICN2 was supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706) and was funded by the CERCA Programme/Generalitat de Catalunya. Part of the present work was performed in the framework of Universitat Autònoma de Barcelona Materials Science Ph.D. program. X.H. thanks China Scholarship Council for scholarship support (201804910551).

International audience; The [Re(bpy)(CO)3Cl] catalyst pioneered by Lehn for the two-electron reduction of CO2 has constantly revealed unique facets in the mechanistic understanding of the selective transformation of CO2. A novel triazole-linked ruthenium photosensitizer and a rhenium catalyst dyad was synthesized and investigated for photo-induced charge accumulation using time-resolved absorption spectroscopy. The triazole bridging ligand promoted weak electronic communication between the two units, resulting in an anodic shift of the reduction potentials of the Re moiety. Upon excitation of the photosensitizer, the first reduction of the catalyst occurred with a fast apparent rate of >5×107 s−1. Using a double-excitation nanosecond pump-pump-probe setup to track the second electron accumulation on the catalytic unit was not conclusive as no observable absorption changes occurred upon the second excitation, suggesting a pathway for an efficient intramolecular reverse electron transfer preventing the two-electron accumulation at the catalyst under our experimental conditions. Nevertheless, under continuous irradiation and with the use of sacrificial electron donors, photocatalytic CO2 reduction assays showed good turnover numbers, hinting at the non-innocent role of byproducts in solution.

International audience

Polyoxothiometalate ions (ThioPOM) are active hydrogen-evolution reaction (HER) catalysts based on modular assembly built from electrophilic clusters {MoSx } and vacant polyoxotungstates. Herein, the dumbbell-like anion [{(PW11 O39 )Mo3 S4 (H2 O)3 (OH)}2 ]8- exhibits very high light-driven HER activity, while the active cores {Mo3 S4 } do not contain any exposed disulfido ligands, which were suspected to be the origin of the HER activity. Moreover, in the catalyst architecture, the two central {Mo3 S4 } cores are sandwiched by two {PW11 O39 }7- subunits that act as oxidant-resistant protecting groups and behave as electron-collecting units. A detailed photophysical study was carried out confirming the reductive quenching mechanism of the photosensitizer [Ir(ppy)2 (dtbbpy)]+ by the sacrificial donor triethanolamine (TEOA) and highlighting the very high rate constant of the electron transfer from the reduced photosensitizer to the ThioPOM catalyst. Such results provide new insights into the field of molecular catalytic systems able to promote high HER activity.

International audience; A new donor–acceptor dyad composed of a BODIPY (4,4′-difluoro-4-bora-3a,4a-diaza-s-indacene) donor and a fullerene C60 acceptor has been synthesized and characterized. This derivative has been prepared using a clickable fullerene building block that bears an alkyne moiety and a maleimide unit. The post-functionalization of the maleimide group by a BODIPY thiol leads to a BODIPY-C60 dyad, leaving the alkyne moiety for further functional arrangement. On the basis of the combination of semi-empirical and density functional theory (DFT) calculations, spectroelectrochemical experiments, and steady-state and time-resolved spectroscopies, the photophysical properties of this new BODIPY-C60 dyad were thoroughly studied. By using semi-empirical calculations, the equilibrium of three conformations of the BODIPY-C60 dyad has been deduced, and their molecular orbital structures have been analyzed using DFT calculations. Two short fluorescence lifetimes were attributed to two extended conformers displaying variable donor–acceptor distances (17.5 and 20.0 Å). Additionally, the driving force for photoinduced electron transfer from the singlet excited state of BODIPY to the C60 moiety was calculated using redox potentials determined with electrochemical studies. Spectroelectrochemical measurements were also carried out to investigate the absorption profiles of radicals in the BODIPY-C60 dyad in order to assign the transient species in pump–probe experiments. Under selective photoexcitation of the BODIPY moiety, occurrences of both energy and electron transfers were demonstrated for the dyad by femtosecond and nanosecond transient absorption spectroscopies. Photoinduced electron transfer occurs in the folded conformer, while energy transfer is observed in extended conformers.

International audience; The Keggin-type polyoxometalate (POM) PW12O403– and the catalytic complex Cp*Rh(bpydc)Cl2 (bpydc = 2,2′-bipyridine-5,5′-dicarboxylic acid) were coimmobilized in the Zr(IV) based metal organic framework UiO-67. The POM is encapsulated within the cavities of the MOF by in situ synthesis, and then, the Rh catalytic complex is introduced by postsynthetic linker exchange. Infrared and Raman spectroscopies, 31P and 13C MAS NMR, N2 adsorption isotherms, and X-ray diffraction indicate the structural integrity of all components (POM, Rh-complex and MOF) within the composite of interest (PW12,Cp*Rh)@UiO-67. DFT calculations identified two possible locations of the POM in the octahedral cavities of the MOF: one at the center of a UiO-67 pore with the Cp*Rh complex pointing toward an empty pore and one off-centered with the Cp*Rh pointing toward the POM. 31P–1H heteronuclear (HETCOR) experiments ascertained the two environments of the POM, equally distributed, with the POM in interaction either with the Cp* fragment or with the organic linker. In addition, Pair Distribution Function (PDF) data were collected on the POM@MOF composite and provided key evidence of the structural integrity of the POM once immobilized into the MOF. The photocatalytic activity of the (PW12,Cp*Rh)@UiO-67 composite for CO2 reduction into formate and hydrogen were evaluated. The formate production was doubled when compared with that observed with the POM-free Cp*Rh@UiO-67 catalyst and reached TONs as high as 175 when prepared as thin films, showing the beneficial influence of the POM. Finally, the stability of the composite was assessed by means of recyclability tests. The combination of XRD, IR, ICP, and PDF experiments was essential in confirming the integrity of the POM, the catalyst, and the MOF after catalysis.

In the present work, we propose a new salicylaldehyde azine based water-soluble fluorescent sensor (PSSA – 4-propoxysulfonate salicylaldehyde azine) dedicated to aluminium(III) detection in aqueous solutions. The introduction of sulfonate functional groups provides the probe with enhanced water-solubility, which is crucial for the direct analysis of polluted samples. We proved that aluminium(III) complexation with PSSA in water induces an aggregation-induced emission enhancement (AIEE) process leading to the formation of well-defined dendritic structures which have been characterized by different analysis techniques (DLS, SEM, and FLIM). A limit of detection towards aluminium(III) of 153 nM has been determined, which is more than one order of magnitude below the World Health Organization (WHO) guideline (≈3.7 μM). Moreover, satisfactory selectivity for this compound has been demonstrated over a large variety of metal cations. Finally, PSSA has been introduced into a digital microfluidic sensor chip, thus providing a sub-micromolar portable detection device devoted to aluminium(III) polluted water samples.

A unique polyoxometalate complex made up of a tetradecanuclear nickel bisphosphonate cluster capping a {SiW9} unit has been characterized. This stable compound exhibits a high hydrogen evolution reaction photocatalytic activity under visible light irradiation via a reductive quenching mechanism.

A highly selective fluorescent sensor based on salicylaldehyde azine derivative for the detection of uranyl cation was developed. The aggregation induced emission characteristics of obtained compounds were investigated and a strong emission of these derivatives was observed upon aggregation in organoaqueous solvent. The emission of these aggregated forms was found to be effectively quenched by uranyl cation. The effect of uranyl was shown to be destructive rather than constructive to the aggregation of the salicylaldehyde azine derivatives. An aggregate-breaking process was proposed to explain the destruction of the aggregates by the complexation with uranyl cation. The sensor showed good selectivity towards uranyl and with a low detection limit up to ppb scale, hence, can be used as an efficient fluorescent sensor for detecting uranyl cation in aqueous solvent.

Herein, new fluorescent sensors based on calix[4]arene-biscrown-6 containing extended coumarin as a fluorophore were synthetized and their photophysical properties were characterized. These compounds display intense absorption and emission spectra in the visible region due to extension of the coumarin system. Moreover, complexation properties of these ligands were reported, and the Calix-COU-Benz-CN ligand was able to selectively detect cesium ions in an organoaqueous solvent. Upon the addition of cesium, a blue-shift in the absorption spectra and an enhancement of the emission spectra were observed. This ligand was incorporated in a microfluidic device for the detection of Cs+ ions, and a detection limit of 1.4 μM was achieved for these ions.

International audience; A unique polyoxometalate complex made up of a tetradecanuclear nickel bisphosphonate cluster capping a {SiW9} unit has been characterized. This stable compound exhibits a high hydrogen evolution reaction photocatalytic activity under visible light irradiation via a reductive quenching mechanism.

Two new fluorescent chemosensors based on calix[4]arene bis(crown-6) bearing coumarin units have been synthesized for the detection of cesium ions in water. The photophysical and complexing properties of these sensors with cesium were investigated using absorption and fluorescence spectroscopies as well as DFT calculations. The coordination of Cs+ by the these ligands induces a better charge transfer between the donor and acceptor groups of the coumarin, resulting in a bathochromic shift in absorption spectra and an enhancement of emission spectra. Both the ligands display an excellent selectivity for Cs+ over other potentially interfering cations such as Na+, Li+, K+, Mg2+, Ca2+ and Sr2+ ions.

International audience; In this article we present a joint study by time-of-flight mass spectroscopy and density functional theory of cobalt protoporphyrin dimer complexes. The main novelty of the experimental part is to reveal the formation of porphyrin dimers that eventually include a chlorine atom. Density functional theory calculations have been performed to shed light on the structural and electronic properties of monomers and dimers that may be formed experimentally. Various geometries of the monomers are analyzed in the two lowest spin states. The electronic structures are examined by means of population analysis relying on the iterative Hirshfeld scheme and the topological analyses of the electron localization function. It is shown that the cobalt ligand bond is purely ionic in the triplet states but shows a noticeable covalent character in the singlet state. Ionization potential of Co-protoporphyrin and binding energies of the chlorine ligand are also reported. Concerning the dimers, several association patterns are investigated for the chlorinated and non-chlorinated complexes. It is found that the structures of the most stable complexes involve four hydrogen bonds between the carboxylic acid moieties of the protoporphyrins. However other association modes are likely to be possible in the experiments.

New fluorescent molecular sensors based on a calix[4]arene biscrown-6 ether as coordination site and BODIPY derivative as signaling unit were synthesized, and their photophysical properties were characterized. The complexation properties of these sensors with potassium and cesium cations were investigated using both steady-state and time-resolved fluorescence methods. The studies show that the sensitivity with cations depends upon the position of substituted coordination site on the BODIPY core. The complexation with cations does not have much effect on the absorption and emission wavelength when the coordination site (calix[4]arene biscrown-6 ether) is introduced at the meso position of the BODIPY core. In contrast, the same calix[4]arene biscrown-6 ether attached via a styryl linker to the α-position of BODIPY core leads to a sensitive sensor for alkali cations thanks to the better conjugation between the coordination site and the BODIPY core. The complexation of cations induces a hypsochromic shift of the absorption and emission maximums due to the diminution of donor character of the oxygen atoms in the coordination site. The stability constants of complexes with potassium and cesium ion were measured.

International audience; The design of robust and inexpensive molecular photocatalysts for the conversion of abundant stable molecules like H2O and CO2 into an energetic carrier is one of the major fundamental questions for scientists nowadays. The outstanding challenge is to couple single photoinduced charge separation events with the sequential accumulation of redox equivalents at the catalytic unit for performing multielectronic catalytic reactions. Herein, double excitation by nanosecond pump-pump-probe experiments was used to interrogate the photoinduced charge transfer and charge accumulation on a molecular dyad composed of a porphyrin chromophore and a ruthenium-based catalyst in the presence of a reversible electron acceptor. An accumulative charge transfer state is unattainable because of rapid reverse electron transfer to the photosensitizer upon the second excitation and the low driving force of the forward photodriven electron transfer reaction. Such a method allows the fundamental understanding of the relaxation mechanism after two sequential photon absorptions, deciphering the undesired electron transfer reactions that limit the charge accumulation efficiency. This study is a step toward the improvement of synthetic strategies of molecular photocatalysts for light-induced charge accumulation and more generally, for solar energy conversion.

Methylviologen (MV2+) is perhaps the most used component as a reversible electron acceptor in photophysical studies. While MV2+ is most commonly implicated as a reversible one-electron mediator, its electrochemical properties clearly evidence two successive one-electron reduction processes. In this report, we have investigated on the light driven two-charge accumulation on MV2+ using a multicomponent system composed of the prototypical molecular photosensitizer [Ru(bpy)3]2+ and MV2+ in the presence of ascorbate as reversible electron donor. The sequential addition of two electrons on the methylviologen was tracked upon sequential excitation of the [Ru(bpy)3]2+ at optimized concentration of the electron acceptor. The charge accumulated state carries an energy of 0.9 eV above the ground state and has a lifetime of ca. 50 μs. We have reached a fairly good global yield of approximately 9% for the two-charge accumulation. This result clearly demonstrates the potential of this simple approach for applications i...

Biomimetic models that contain elements of photosynthesis are fundamental in the development of synthetic systems that can use sunlight to produce fuel. The critical task consists of running several rounds of light-induced charge separation, which is required to accumulate enough redox equivalents at the catalytic sites for the target chemistry to occur. Long-lived first charge-separated state and distinct electronic signatures for the sequential charge accumulated species are essential features to be able to track these events on a spectroscopic ground. Herein, we use a double-excitation nanosecond pump-pump-probe experiment to interrogate two successive rounds of photo-induced electron transfer on a molecular dyad containing a naphthalene diimide (NDI) linked to a [Ru(bpy)3 ](2+) (bpy=bipyridine) chromophore by using a reversible electron donor. We report an unprecedented long-lived two-electron charge accumulation (t=200 μs).

In this present article, we present recent development of fluorescent molecular sensors based on calixarene for the detection of various species including cations, anions, and neutral molecules. The observed modulation of the fluorescence is because of perturbation of several photoinduced processes such as electron transfer, energy transfer, charge transfer, excimer formation and disappearance, chemodosimeter, and aggregation effect. The discussion clearly indicates the role of calixarene framework in developing selective and sensitive molecular sensor for a particular type of analyte.

International audience; The development of highly selective sensors for potassium is of great interest in biology. Two new hydrosoluble potassium sensors (Calix-COU-Alkyne and Calix-COU-Am) based on a calix[4]arene bis(crown-6) and an extended coumarin were synthesized and characterized. The photophysical properties and complexation studies of these compounds have been investigated and show high molar extinction coefficients and high fluorescence quantum yields. Upon complexation with potassium in the millimolar concentration range, an increase of one- and two-photon fluorescence emission is detected. A twofold fluorescence enhancement is observed upon excitation at λ=405 nm. The ligands present excellent selectivity for potassium in the presence of various competitive cations in water and in a physiological medium. The photophysical properties are not affected by the presence of a large amount of competing cations (Na+ , Ca2+ , Mg2+ , etc.). Ex vivo measurements on mouse hippocampal slices show that Calix-COU-Alkyne accumulates extracellularly and does not alter the neuronal activity. Furthermore, the sensor can be utilized to monitor slow extracellular K+ increase induced by inhibition of K+ entry into the cells.

A new fluorescent molecular sensor for Hg2+ based on the phosphane sulfide derivative exhibits a very low detection limit in an aqueous medium (3.8 nM) with a very high selectivity over other interfering cations. The reversibility of the complexation process was also examined and was found to be successful. [structure: see text]

International audience; The design of a new class of fluorophores is presented. Some push– pull chromophores (D–p–A) containing polyphenylethynyl units and a phosphane oxide moiety were efficiently prepared from common intermediates. Straightforward syntheses gave novel one-armed, rod-shaped and three-armed, star-shaped fluorophores. The optical properties of the resulting star-shaped derivatives were evaluated, showed high fluorescence quantum yields, and their excitation induces very efficient charge redistribution. Moreover, thanks to their push–pull character, the molecules exhibited significant second-order NLO properties with good transparency, up to 67·1030 esu at 1907 nm, with an absorption lmax at 369 nm. The effect of the donor group and of the number of phenylethynyl arms have been studied in this work.

Hemoprotein mimics, cobalt picket fence porphyrins have been prepared in the gas phase as neutral molecules for the first time. Their ligation properties have been studied with 1-methylimidazole and compared with those of other cobalt porphyrins, tetraphenyl porphyrin, and cobalt protoporphyrin IX chloride, in view of studying the sterical properties of the ligation. It is shown that the cobalt picket fence porphyrin can only accept one 1-methylimidazole ligand in contrast to less sterically crowded porphyrins like cobalt tetraphenylporphyrin that present two accessible ligation sites. The femtosecond dynamics of these ligated systems have been studied after excitation at 400 nm, in comparison with the unligated ones. The observed transients are formed in much shorter times, 30 fs for the ligated species, as compared to free species (100 fs), supporting the porphyrin to metal charge transfer nature of these transients. The similar decays of the ligated transients

International audience; The ultrafast dynamics of copper tetraphenylporphyrin (CuTPP), copper octaethylporphyrin (CuOEP), and of the free base tetraphenylporphyrin (H2TPP), excited in the S2 state have been investigated in the gas phase by femtosecond pump/probe experiments. The porphyrins were excited in the Soret band at 400 nm. Strikingly, the S2-S1 internal conversion in H2TPP is very rapid (110 fs), as compared to that of ZnTPP (600 fs), previously observed. In turn, CuTPP and CuOEP, excited in S2, follow an efficient and different relaxation pathway from that of other open-shell metalloporphyrins. These two molecules exhibit a sequential four-step decay ending on a slow evolution in the nanosecond range 2S2 → 2CT → 2T → 2Ground State. This latter evolution is linked to the formation of the 2T, tripdoublet state in CuTPP, observed in the condensed phase. It is shown that an intermediate charge transfer state plays a crucial role in linking the porphyrin centered 1ππ* and 3ππ* configurations. A simple model is presented that allows a rapid evolution between these two configurations, via coupling of the porphyrin π system with the free d electron on the copper. The mechanism obviates the need for the spin orbit coupling within the porphyrin. The result is that these copper porphyrins can exhibit an ultrafast apparent intersystem crossing, unprecedented for organic molecules.

International audience; The observation of the light absorption of neutral biomolecules has been made possible by a method implemented for their preparation in the gas phase, in supersonically cooled molecular beams, based upon the work of Focsa et al. [C. Mihesan, M. Ziskind, B. Chazallon, E. Therssen, P. Desgroux, S. Gurlui, and C. Focsa, Appl. Surf. Sci. 253, 1090 (2006)]10.1016/j.apsusc.2006.01.082. The biomolecules diluted in frozen water solutions are entrained in the gas plume of evaporated ice generated by an infrared optical parametric oscillators (OPO) laser tuned close to its maximum of absorption, at ∼3 μm. The biomolecules are then picked up in the flux of a supersonic expansion of argon. The method was tested with indole dissolved in water. The excitation spectrum of indole was found cold and large clusters of indole with water were observed up to n = 75. Frozen spinach leaves were examined with the same method to observe the chlorophyll pigments. The Qy band of chlorophyll a has been observed in a pump probe experiment. The Qy bands of chlorophyll a is centred at 647 nm, shifted by 18 nm from its position in toluene solutions. The ionization threshold could also be determined as 6.1 ± 0.05 eV.

Biomimetic molecules are systems that provide a direct and simpler reproduction of a molecular process essential to the living world, i.e. they mimic a function or a structure of a biomolecular edifice. The idea is to isolate this process and allow a selective study of a specific function by physicochemical methods, in a reductionist way. In that respect, gas phase studies of biomolecules are ideal, since they allow the application of a variety of highly sensitive and selective tools to the study of these model systems: mass spectrometry, photoelectron spectroscopy, for example, provided that the molecular system has been vaporised. In addition, the system is studied in absence of solvent, which greatly simplifies the interpretation of the fundamental effects and consequently allows to infer the effects of the medium since, in the gas phase solvents can be introduced in a gradual manner via clusters. Also gas phase measurements allow a direct comparison with results from quantum chemistry calculations. Great progresses have been fuelled in this direction by the developments of mass spectrometry. The studies in the gas phase have been mostly dedicated to the elucidation of the basic structure of the building blocks of proteins, i.e. small peptides (Simons, 2004). In turn, other biological functions have been less studied by the gas phase biomimetic approach. Hematoproteins hosting hemoporphyrins (the heme, see fig 1) are ideal systems to examine in this way, since they are at the heart of the oxygen and small molecules transport within blood and that their active site is localised very precisely on the metal atom embedded in their central porphyrin. Thus, if one studies the active porphyrinic site of myoglobin at short time scales (in the subpicosecond time domain), the interaction with the environing protein (globin myoglobin) can be minimised. In hemoproteins, the attachment of oxygen to the iron of the heme is a complex process involving a potential barrier. This barrier results from the crossing of two surfaces of

The photophysical properties of a complex based on diphenylphosphanoethane (DPPE) fluorescent ligands linked to a europium ion have been investigated by different spectroscopic methods. Upon complexation with europium, the interaction of the phosphane oxide group with europium leads to a red shift of the absorption spectrum and a strong quenching of the ligand emission. The typical sensitized emission of Eu(3+) is observed upon excitation of the ligand with a fluorescence quantum yield of 1%. Time-resolved absorption and emission experiments have been performed in order to investigate the photophysical mechanism involved in this complex. Photophysical studies show that an energy-transfer mechanism occurs from both the first excited singlet and triplet states of the ligand, and the population of the europium ion to the (5)D(1) state takes place, from which the (5)D(0) state is populated. Additionally, electron transfer from the excited singlet state of the ligand to the europium ion appears as a very efficient process.

A series of fluorescent phosphane oxide derivatives based on diphenylphosphanoethane (DPPE) and diphenylphosphanomethane (DPPM) skeletons has been prepared by means of Grignard reactions and Sonogashira cross-couplings. The photophysical properties and the linear and nonlinear spectra of these compounds have been investigated. An edge-to-face conformation resulting in the formation of an excimer was confirmed by fluorescence lifetime measurements of these multichromophoric derivatives. Upon complexation with heavy metal ions such as Pb2+ and Cd2+, a red shift of the one- and two-photon excitation spectra was observed in the absorption and emission spectra. Furthermore, enhancement of the electron-withdrawing character of the phosphane oxide resulted in a significant enhancement of the two-photon absorption cross-section, leading to the first biphotonic Cd2+ sensors combining high affinity for Cd2+, large two-photon absorption cross-sections, and significant enhancement of the two-photon excited fluorescence in the presence of the cation. Such derivatives are highly promising for incorporation into devices for the detection of heavy metal ions in water and effluents.

International audience

International audience; The time evolution of electronically excited heme (iron II protoporphyrin IX, [Fe-II PP]) and its associated salt hemin (iron III protoporphyrin IX chloride, [Fe-III PP-Cl]), has been investigated for the first time in the gas phase by femtosecond pump-probe spectroscopy. The porphyrins were excited at 400 nm in the S-2 state (Soret band) and their relaxation dynamics was probed by multiphoton ionization at 800 nm. This time evolution was compared with that of the excited state of zinc protoporphyrin IX [Zn PP] whose S2 excited state likely decays to the long lived S-1 state through a conical intersection, in less than 100 fs. Instead, for [Fe-II PP] and [Fe-III PP-Cl], the key relaxation step from S-2 is interpreted as an ultrafast charge transfer from the porphyrin excited orbital pi* to a vacant d orbital on the iron atom (ligand to metal charge transfer, LMCT). This intermediate LMCT state then relaxes to the ground state within 250 fs. Through this work a new, serendipitous, preparation step was found for Fe II porphyrins, in the gas phase.

A series of fluorescent sensor molecules based on a phosphane sulfide derivative were designed and synthesized. The effect of the distance between the complex entities as well as the number and the length of fluorophores was investigated using both steady-state and time-resolved fluorescence methods. The complexation behavior of these sensor molecules, which have a distinct affinity for Hg(2+), is reported. The coordination of Hg(2+) induces a photoinduced electron transfer from fluorophore to the complexed mercury and results in a significant decrease of the fluorescence. Theses sensors exhibit very low detection limits in CH(3)CN/H(2)O (80/20 v:v) and excellent sensitivity to Hg(2+) over other potentially interfering cations such as Na(+), K(+), Mg(2+), Ca(2+), Cu(2+), Ag(+), Zn(2+), Cd(2+) and Pb(2+).