Synthesis of Redox-Active Photochromic Phenanthrene Derivatives.

A phenanthrene unit has been functionalized by several methylthiophene units in order to bring it a photochromic behavior. These compounds were characterized by NMR, absorption and emission spectroscopies, theoretical calculations as well as cyclic voltammetry. The association of a phenanthrene group with a photochromic center could open the door to a new generation of organic field-effect transistors.

New Insights into the Redox Properties of Pyridinium Appended 1,2-Dithienylcyclopentenes.

The optical and redox properties of a methyl pyridinium appended 1,2-dithienylethene photochromic derivative have been thoroughly investigated. A complex multi-step photo/redox mechanism is proposed for the closed isomer on the ground of spectro-electrochemical and theoretical data. The generated compounds are not stable over the time because of chemical reactions associated to the redox processes and a new dithienylethene derivative incorporating a seven-membered ring has been isolated and characterized.

Synthesis of a Negative Photochrome with High Switching Quantum Yields and Capable of Singlet-Oxygen Production and Storage.

A dimethyldihydropyrene (DHP) photochromic unit has been functionalized by donor (triphenylamine group) and acceptor (methylpyridinium) substituents. This compound was characterized by NMR, absorption and emission spectroscopies as well as cyclic voltammetry, and its properties were rationalized by theoretical calculations. The incorporation of both electron-donor and -withdrawing groups at the photochromic center allows i) an efficient photo-isomerization of the system when illuminated at low energy (quantum yield: Φc-o =13.3 % at λex =660 nm), ii) the reversible and quantitative formation of two endoperoxyde isomers when illuminated under aerobic conditions at room temperature, and iii) the storage and production of singlet oxygen. The photo-isomerization mechanism was also investigated by spin-flip TD-DFT (SF-TD-DFT) calculations.

Photo-/Electroinduced Irreversible Isomerization of 2,2'-Azobispyridine Ligands in Arene Ruthenium(II) Complexes.

Novel arene RuII complexes containing 2,2'-azobispyridine ligands were synthesized and characterized by using 1 H and 13 C NMR spectroscopy, UV/vis spectroscopy, electrochemistry, DFT calculations and single-crystal X-ray diffraction. Z-configured complexes featuring unprecedented seven-membered chelate rings involving the nitrogen atom of both pyridines were isolated and were shown to undergo irreversible isomerization to the corresponding E-configured five-membered chelate complexes in response to light or electrochemical stimulus.

Complexation of C-Functionalized Cyclams with Copper(II) and Zinc(II): Similarities and Changes When Compared to Parent Cyclam Analogues.

Herein, we report a comprehensive coordination study of the previously reported ligands cyclam, CB-cyclam, TMC, DMC, and CB-DMC and of their C-functional analogues, cyclam-E, CB-cyclam-E, TMC-E, DMC-E, and CB-DMC-E. This group of ligands includes cyclam, cross-bridged cyclams, their di- or tetramethylated derivatives, and the analogues bearing an additional hydroxyethyl group on one ß-N position of the ring. The Cu(II) and Zn(II) complexes of these macrocycles have been highlighted previously for the biological interest, but the details of their structures in the solid state and in solution remained largely unexplored. In particular, we analyzed the impact that adding noncoordinating N-methyl and C-hydroxyethyl functionalities has in the structures of the complexes. All the Cu(II) and Zn(II) complexes were synthesized and investigated using single crystal X-ray diffraction and NMR, electronic absorption, and EPR spectroscopies, along with DFT studies. Dissociation kinetics experiments in acidic conditions and electrochemical studies were also performed. Special attention was paid to analyze the different configurations present in solution and in the solid state, as well as the impact of the C-appended hydroxyethyl group on the coordination behavior. Various ratios of the trans-I, trans-III, and cis-V configurations have been observed depending on the degree of N-methylation and the presence of the ethylene cross-bridge.

Dependency of the Dimethyldihydropyrene Photochromic Properties on the Number of Pyridinium Electron-Withdrawing Groups.

Photochromic dimethyldihydropyrenes substituted with electron-withdrawing pyridinium groups have shown an increase of photo-induced ring-opening efficiency and a light sensitivity that is red shifted relative to the unsubstituted compound. However, a recently synthesized tetrapyridinium derivative showed a considerable decrease of the photo-isomerization quantum yield relative to the monopyridinium and bispyridinium derivatives. We provide a rationale for this unexpected photochemical behavior based on the comparative theoretical investigations of the relevant excited states of these systems. In particular, we found that the nature and order of the lowest two excited states depend on the number of pyridinium groups and on the symmetry of the system. While the lowest S1 excited state is photo-active in the monopyridinium and bispyridinium derivatives, the photo-isomerizing state is S2 in the reference unsubstituted compound and both S1 and S2 lead to isomerization in the tetrapyridinium derivative, albeit with a low efficiency. In the latter derivative, the photo-isomerization is hindered by the particular S1 /S2 conical intersection topology.

Structural Study of Polystyrene-b-poly(acrylic acid) Micelles Complexed with Uranyl: A SAXS Core-Shell Model Analysis.

The interactions between natural colloidal organic matter and actinides in solutions are complex and not fully understood. In this work, a crew-cut polystyrene-b-poly(acry1ic acid) (PS-b-PAA) micelle is proposed as a model particle for humic acid (HA) colloid with the aim to better understand the sequestration, aggregation, and mobility of HA colloids in the presence of uranyl ions. The effects of uranyl ions on the structure of PS29k-b-PAA5k micelles in aqueous solution were mainly investigated by synchrotron small-angle X-ray scattering. A core-shell model, accounting for the thickness and contrast changes of the PAA corona induced by the adsorption of uranyl, was employed to analyze the scattering data. A combination of transmission electron microscopy, dynamic light scattering, and zetametry showed a strong affinity of uranyl ions to PAA segments in water at pH 4-5 that resulted in the shrinkage and improved contrast of the PAA corona, as well as colloidal destabilization at a high uranyl concentration.

Redox-Responsive Colloidal Particles Based on Coordination Polymers Incorporating Viologen Units.

Colloidal particles based on supramolecular polymers are emerging as promising functional materials because of their intrinsic dynamic features and the possibility of stimuli responsivity. In this work, ≈200 nm self-assembled redox-responsive colloidal particles made of 1D-coordination polymers were readily prepared. In these metallopolymers, organic entities made of bis(viologen) groups covalently associated with terpyridine units are spontaneously bridged by Zn2+ cations through the formation of coordination bonds. The properties of these particles were analyzed and their redox activities investigated. Upon reduction of the viologen units, the formation of π-dimers between the reduced viologen moieties was demonstrated by spectroscopic experiments. It was shown that intermolecular π-dimers (i.e., between different polymer chains) that do not exist in homogeneous polymer solutions were, nevertheless, formed in the particle's structure because of the effects of confinement. The presence of these π-dimers allows stabilization of the charge in the colloids.

Electronic Excited States and UV-Vis Absorption Spectra of the Dihydropyrene/Cyclophanediene Photochromic Couple: a Theoretical Investigation.

Dihydropyrene (DHP)/cyclophanediene (CPD) is a fascinating photoswitchable organic system displaying negative photochromism. Upon irradiation in the visible region, the colored DHP can be converted to its open-ring CPD colorless isomer, which can be converted back to DHP by UV light. DHP and CPD thus possess very different absorption spectra whose absorption bands have never been assigned in detail so far. In this work, we characterize the vertical electronic transitions of the first six and seven excited states of DHP and CPD, respectively, aiming for a realistic comparison with experiment. We used state-of-the-art electronic structure methods [e.g., complete active space second-order perturbation theory (CASPT2), n-electron valence-state perturbation theory (NEVPT2), extended multiconfigurational quasi-degenerate perturbation theory (XMCQDPT2), and third-order algebraic diagrammatic construction ADC(3)] capable of describing differential electron correlation. Vertical transition energies were also computed with time-dependent density functional theory (TD-DFT) and compared to these accurate methods. After the reliability of TD-DFT was validated for the main optical transitions, this efficient method was used to simulate the absorption spectra of DHP and CPD in the framework of the Franck-Condon Herzberg-Teller approximation and also using the nuclear ensemble approach. Overall, for both methods, the simulated absorption spectra reproduce nicely the main spectral features of the DHP and CPD isomers, that is, the main four absorption bands of increasing intensity of DHP and the absorption rise below 300 nm for CPD.

Dynamic Molecular Metamorphism Involving Palladium-Assisted Dimerization of π-Cation Radicals.

A dynamic supramolecular approach is developed to promote the π-dimerization of viologen radicals at room temperature and in standard concentration ranges. The approach involves cis- or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. Based on detailed spectroscopic, electrochemical and computational data, we show that the one-electron electrochemical reduction of the viologen units in different dynamic metal/ligand mixtures leads to the formation of the same intramolecular π-dimer, regardless of the initial environment around the metallic precursor and of the relative ratio between metal and ligand initially introduced in solution. The large-scale electron-triggered reorganization of the building blocks introduced in solution thus involves drastic changes in the stoichiometry and stereochemistry of the palladium/viologen complexes proceeding in some cases through a palladium centered trans→cis isomerization of the coordinated ligands.

Redox-Induced Molecular Metamorphism Promoting a Sol/Gel Phase Transition in a Viologen-Based Coordination Polymer.

We have developed a strategy enabling control over the organization of ditopic molecular tectons within a palladium-based self-assembled system. The key electron-responsive sub-unit is a viologen-based mechanical hinge that can toggle under electric stimulation between a folded and a stretched position, the driving force of the folding motion being the π-dimerisation of the electrogenerated viologen cation radicals. The title ditopic tecton features two planar, N2-type, triazole/pyridine-based bidentate binding units, providing the tecton with the ability to chelate two palladium ions both in its folded and in its elongated conformations. Association of this ditopic redox-responsive tecton with palladium to form 1D self-assembled architectures undergoing large scale reorganizations in solution under electric stimulation, has been established on the ground of spectroscopic, electrochemical, spectro-electrochemical and rheological data. Our result reveal that addition of metal leads to a significant stabilization of the π-dimer species in solution and that the redox-triggered reorganisation of the tectons comes along in suitable conditions with a macroscopic sol/gel-type phase transition.

Redox-Triggered Folding of Self-Assembled Coordination Polymers incorporating Viologen Units.

We report the study of stimuli-responsive ZnII and FeII coordination polymers (MC34+ or MC24+ with M=Fe2+ or Zn2+ ). These soluble metallopolymers were formed spontaneously by reaction of an organic ligand (C34+ or C24+ ) with one molar equivalent of metal ions. The C34+ and C24+ ligands incorporate two chelating terpyridine groups bridged by a redox responsive hinge featuring two viologen units (viologen=N,N'-dialkyl-4,4'-bipyridinium) linked either with propyl (C34+ ) or ethyl (C24+ ) chains. The viologen units in the polymer chains were reduced (1 e- per viologen group) either by bulk electrolysis or by visible-light irradiation carried out in the presence of a photosensitizer. The 1 e- reduction of the viologen units in the MC24+ polymers induced a slight decrease in the viscosity of the solutions due to a modification of the overall charge carried by the metallopolymers. In strong contrast, reduction of coordination polymers involving propyl linkers (MC34+ ) led to a remarkable increase (≈+400 %) in observed viscosity. This reversible effect was attributed to a folding of the polymer chains triggered by π-dimerization of the photo-generated viologen cation radicals.

The Advantages of Cyclic Over Acyclic Carbenes To Access Isolable Capto-Dative C-Centered Radicals.

A cyclic and an acyclic di(amino)carbene as well as a cyclic and an acyclic (alkyl)(amino)carbene cleanly react with benzoyl chloride to give the corresponding adducts 1+cyc , 1+acy , 2+cyc , and 2+acy , respectively. The reduction of 1+cyc and 2+cyc derived from cyclic carbenes affords the corresponding radicals 1cyc and 2cyc that are stable at room temperature. In contrast, radicals 1acy and 2acy , derived from acyclic carbenes, cannot be isolated. It is shown that 1acy is as thermodynamically stabilized as its cyclic counterpart 1cyc , but its instability is the result of ß-hydrogens of the nitrogen substituent, along with the enhanced flexibility around C-N bonds, which allow for a H. -migration-elimination process. Radical 2acy is thermodynamically unstable, and undergoes disproportionation into the corresponding iminium 2+acy and enolate 2-acy . This is due to the excessive steric hindrance, which prevents electron-delocalization on the NCCO fragment, and thus, the capto-dative stabilization. This work suggests general guidelines for the design of highly persistent (amino)(carboxy)radicals, especially by emphasizing the key advantage of cyclic patterns.

Efficient Photoswitch System Combining a Dimethyldihydropyrene Pyridinium Core and Ruthenium(II) Bis-Terpyridine Entities.

Terpyridine ruthenium complexes linked to the dimethyldihydropyrene (DHP) photochromic unit have been synthesized and fully characterized by cyclic voltammetry and absorption and emission spectroscopy. The study of the photoisomerization reaction undergone by the DHP motif under visible light irradiation is reported. In comparison to previous work, the introduction of an electron-withdrawing pyridinium spacer between the chelating terpyridine unit and the DHP skeleton has considerably tuned the photochromic properties of the free ligands and their corresponding complexes in term of time response and photoreversibility. A rapid, reversible, and complete conversion between the closed and the open forms has been clearly evidenced under visible light irradiation. Only slight perturbations have been induced by the presence of ruthenium centers. Experimental findings and their interpretation have been supported by theoretical calculations.

Electron-Triggered Metamorphism in Porphyrin-Based Self-Assembled Coordination Polymers.

Viologen-centered electron transfer is used to trigger a complete dissociation of a porphyrin-based supramolecular architecture. In the oxidized state, self-assembly is induced by iterative association of individual porphyrin-based tectons. Dissociation of the self-assembled species is actuated upon changing the redox state of the bipyridium units involved in the tectons from their dicationic state to their radical cation state, the driving force of the disassembling process being the formation of an intramolecularly locked conformation partly stabilized by π-dimerization of both viologen cation radicals.

A multi-addressable switch based on the dimethyldihydropyrene photochrome with remarkable proton-triggered photo-opening efficiency.

A series of photochromic derivatives based on the trans-10b,10c-dimethyl-10b,10c-dihydropyrene (DHP, "closed form") skeleton has been synthesized and their photoisomerization leading to the corresponding cyclophanediene (CPD, "open form") isomers has been investigated by UV/Vis and (1) H NMR spectroscopies. Substitution of the DHP core with electron-withdrawing pyridinium groups was found to have major effects on the photoisomerization efficiency, the most remarkable examples being to enhance the quantum yield of the opening reaction and to allow fast and quantitative conversions at much lower radiant energies. This effect was rationalized by theoretical calculations. We also show that the reverse reaction, that is, going from the open form to the closed form, can be electrochemically triggered by oxidation of the CPD unit and that the photo-opening properties of pyridine-substituted DHPs can be efficiently tuned by protonation, the system behaving as a multi-addressable molecular switch. These multi-addressable photochromes show promise for the development of responsive materials.

Optical modulation of cell nucleus penetration and singlet oxygen release of a switchable platinum complex.

The activation of anticancer molecules with visible light constitutes an elegant strategy to target tumors and to improve the selectivity of treatments. In this context, we report here a visible-light activatable bis-platinum complex (DHP-Pt2) incorporating an organic photo-switchable ligand based on the dimethyldihydropyrene moiety. Illumination of this metal complex with red light (660 nm) under air readily produces the corresponding endoperoxide form (CPDO2-Pt2). These two metal complexes exhibit different DNA binding properties and, more importantly, we show that only the photogenerated CPDO2-Pt2 is able to penetrate into cancer cell nuclei, where it is then capable of releasing cytotoxic singlet oxygen. This study represents the first proof-of-concept showing that dimethyldihydropyrene derivatives can be used to transport and deliver singlet oxygen into cancer cell nuclei upon visible-light activation.

Design and synthesis of 4-amino-2',4'-dihydroxyindanone derivatives as potent inhibitors of tyrosinase and melanin biosynthesis in human melanoma cells.

Melanogenesis inhibition constitutes a privileged therapeutic solution to treat skin hyperpigmentation, a major dermatological concern associated with the overproduction of melanin by human tyrosinase (hsTYR). Despite the existence of many well-known TYR (tyrosinase) inhibitors commercialized in skin formulations, their hsTYR-inhibition efficacy remains poor since most of them were investigated over mushroom tyrosinase (abTYR), a model with low homology relative to hsTYR. Considering the need for new potent hsTYR inhibitors, we designed and synthesized a series of indanones starting from 4-hydroxy compound 1a, one of the two most active derivatives reported to date against the human enzyme, together with marketed thiamidol. We observed that analogues featuring 4-amino and 4-amido-2',4'-dihydroxyindanone motifs showed two-to ten-fold increase in activity over human melanoma MNT-1 cell lysates, and a ten-fold improvement in a 4-days whole-cell experiment, compared to parent analogue 1a. Molecular docking investigation was performed for the most promising 4-amido derivatives and suggested a plausible interaction pattern with the second coordination sphere of hsTYR, notably through hydrogen bonding with Glu203, confirming their impact in the binding mode with hsTYR active site.

Charge transport in photoswitchable dimethyldihydropyrene-type single-molecule junctions.

The conductance properties of a photoswitchable dimethyldihydropyrene (DHP) derivative have been investigated for the first time in single-molecule junctions using the mechanically controllable break junction technique. We demonstrate that the reversible structure changes induced by isomerization of a single bispyridine-substituted DHP molecule are correlated with a large drop of the conductance value. We found a very high ON/OFF ratio (>10(4)) and an excellent reversibility of conductance switching.