Light- and Temperature-Controlled Hybridization, Chiral Induction and Handedness of Helical Foldamers.

Helical foldamers have attracted much attention over the last decades given their resemblance to certain biomacromolecules and their potential in domains as different as pharmaceutics, catalysis and photonics. Various research groups have successfully controlled the right- or left- handedness of these oligomers by introducing stereogenic centers through covalent or non-covalent chemistry. However, developing helical structures whose handedness can be reversibly switched remains a major challenge for chemists. To date, such an achievement has been reported with light-responsive single-stranded foldamers only. Herein, we demonstrate that grafting a unidirectional motor onto foldamer strands constitutes a relevant strategy to i) control the single or double helical state of a foldamer, ii) switch on the chiral induction process from the motor to the helical strands and iii) select the handedness of double helical structures through photochemical and thermal stimulations.

Intermolecular Anionic Mixed-Valence and π-Dimer Complexes of Ortho-Pentannulated BisAzaCoroneneDiimides.

This study reports the serendipitous discovery of intermolecular anionic mixed-valence (MV) and π-dimer species in ortho-pentannulated BisAzaCoroneneDiimides (BACDs) during their electrochemical reduction in a non-aqueous solvent. A library of nitrogen-containing extended PDIs was synthesized via an aza-benzannulation reaction followed by a Pd-catalysed ortho-pentannulation reaction. Ortho-pentannulated BACDs revealed strong aggregation abilities in solution. Concentration-dependent UV-vis absorption spectra, variable temperature 1H NMR experiments, and atomic force microscopy coupled to molecular dynamics support their self-assembly into columnar aggregates. Cyclic voltammetry experiments in dichloromethane reveal prominent splitting of the first reduction wave, attributed to the formation of unprecedented intermolecular anionic MV and π-dimers in organic solvent. These species were thoroughly characterized by real-time spectroelectrochemistry, electrochemical simulations and theoretical calculations. Remarkably, this work underscores the tuneable nature of AzaBenzannulatedPerylene Diimides (AzaBPDIs) and BACDs, emphasizing their potential as a promising scaffold for designing supramolecular materials with long-range radical anion delocalization. The observation of this phenomenon provides insights into the fundamental behaviour of supramolecular organic semiconductors, thereby paving the way for the development of novel electronic devices and electron-deficient materials.

Heavy-atom-free π-twisted photosensitizers for fluorescence bioimaging and photodynamic therapy.

As the field of preclinical research on photosensitizers (PSs) for anticancer photodynamic therapy (PDT) continues to expand, a focused effort is underway to develop agents with innovative molecular structures that offer enhanced targeting, selectivity, activation, and imaging capabilities. In this context, we introduce two new heavy-atom-free PSs, DBXI and DBAI, characterized by a twisted π-conjugation framework. This innovative approach enhances the spin-orbit coupling (SOC) between the singlet excited state (S1) and the triplet state (T1), resulting in improved and efficient intersystem crossing (ISC). Both PSs are highly effective in producing reactive oxygen species (ROS), including singlet oxygen and/or superoxide species. Additionally, they also demonstrate remarkably strong fluorescence emission. Indeed, in addition to providing exceptional photocytotoxicity, this emissive feature, generally lacking in other reported structures, allows for the precise monitoring of the PSs' distribution within specific cellular organelles even at nanomolar concentrations. These findings underscore the dual functionality of these PSs, serving as both fluorescent imaging probes and light-activated therapeutic agents, emphasizing their potential as versatile and multifunctional tools in the field of PDT.

Designing Dual-State and Aggregation-Induced Emissive Luminogens from Lignocellulosic Biosourced Molecules.

Utilizing lignocellulosic biosourced platforms, we synthesized novel cyanostilbene (CS) derivatives featuring the 3,4-dimethoxyphenyl moiety. These derivatives were investigated for their emission properties in both solution and solid states. The two simple CS derivatives exhibit very weak luminescence in solution but significant luminescence in the solid state, indicating distinct Aggregation-Induced Emission (AIE) characteristic. Furthermore, combining these two CS units, without conjugation and with quasi perpendicular orientation, results in a Dual-State Emission (DSE) fluorophore showing luminescence both in solution and solid states. X-ray crystallography studies on the solid-state compounds reveal a structure-emission relationship, demonstrating that the colour emission correlates with the conformations adopted by the molecules in the solid state, which influence the type of stacking.

Driving Triplet State Population in Benzothioxanthene Imide Dyes: Let's twist!

Controlling the formation of photoexcited triplet states is critical for many (photo)chemical and physical applications. Here, we demonstrate that a permanent out-of-plane distortion of the benzothioxanthene imide (BTI) dye promotes intersystem crossing by increasing spin-orbit coupling. This manipulation was achieved through a subtle chemical modification, specifically the bay-area methylation. Consequently, this simple yet efficient approach expands the catalog of known molecular engineering strategies for synthesizing heavy atom-free, dual redox-active, yet still emissive and synthetically accessible photosensitizers.

Perovskite versus Nonperovskite: Modulating the Nature and Optical Properties of One-Dimensional Chiral Lead-Bromide Networks.

In the last 5 years, low-dimensional chiral metal-halide semiconductors have attracted great interest in the generation of chiroptical activity. Among this new family of materials, one-dimensional (1D) networks have appeared as the best candidates for strong circular dichroism (CD) and circularly polarized luminescence (CPL). Here, we present a new family of 1D chiral lead-bromide materials prepared from organic S/R/rac-1-hydroxypropyl-2-ammonium (S/R/rac-HP2A) cations. The presence or absence of polarity in the crystal structure as well as the perovskite or nonperovskite nature of the inorganic network depends on the initial stoichiometry of metal-halide salt and chiral amine during the crystallization. The perovskite-type networks exhibit strong CD and second harmonic generation (SHG) responses, while the nonperovskite compounds show the presence of polymorphism in the crystal phase and weak natural optical activity in the final material. These results underline the impact of synthetic conditions and thin film morphology on the structural and optical properties of metal-halide hybrid networks.

Chiral Truxene-Based Self-Assembled Cages: Triple Interlocking and Supramolecular Chirogenesis.

Incorporating chiral elements in host-guest systems currently attracts much attention because of the major impact such structures may have in a wide range of applications, from pharmaceuticals to materials science and beyond. Moreover, the development of multi-responsive and -functional systems is highly desirable since they offer numerous benefits. In this context, we describe herein the construction of a metal-driven self-assembled cage that associates a chiral truxene-based ligand and a bis-ruthenium complex. The maximum separation between both facing chiral units in the assembly is fixed by the intermetallic distance within the lateral bis-ruthenium complex (8.4 Å). The resulting chiral cavity was shown to encapsulate polyaromatic guest molecules, but also to afford a chiral triply interlocked [2]catenane structure. The formation of the latter occurs at high concentration, while its disassembly could be achieved by the addition of a planar achiral molecule. Interestingly the planar achiral molecule exhibits induced circular dichroism signature when trapped within the chiral cavity, thus demonstrating the ability of the cage to induce supramolecular chirogenesis.

Tuning the Solid State Luminescence of Benzofuran-Cyanostilbenes by Functionalization with Electron Donors or Acceptors.

Three series of linear extended benzofuran derivatives associating cyanovinyl unit and electron withdrawing systems such as paracyanophenyl (series 1) and pentafluorophenyl (series 2) units or the electron donor 3,4-dimethoxyphenyl (series 3) moiety have been prepared. The donor character of the benzofuran part is adjusted either without modifying the conjugation by adding electron-donating methoxy groups to positions 5 and 6 of the benzofuran (compounds BF2 and BF3) or by increasing the extension of the conjugation with the naphthofuran unit (BF4), and by the insertion of a furan ring between the benzofuran and the cyanovinylene bond (BF5). While most of the compounds show very low emission in solution, microcrystalline powders of almost all compounds show middle at strong emissions under excitation at 350-400 nm with emission colors ranging from blue - green to red. It is shown that this variation of the emission colors is essentially due to the type of stacking of the molecules in the solids for series 1 and 2. For series 3, it is above all the extension of the conjugation of the compounds which leads to the red shift.

Chemistry in the Molten State: Opportunities for Designing and Tuning the Emission Properties of Halide Perovskites.

A series of monolayered lead halide hybrid perovskites (HO2C(CH2)n-1NH3)2PbX4, named (Cn)2PbX4 (n = 4-6, X = Cl, Br), exhibiting a low congruent melting temperature (Tm) (Tm = 130 °C for (C4)2PbBr4), high stability in the molten state, and whitish type emission, are reported. From the synthesis in the molten state, rare solid solutions of mixed organic cations (Cn1-xCn'x)2PbX4 (n, n' = 4-6; X = Cl, Br; 0 ≤ x ≤1) as well as solid solutions of mixed halides (Cn)2Pb(X1-yX'y)4 (n = 4-6; X, X' = Cl, Br; 0 ≤ y ≤1) have been prepared and characterized (thermal behavior, powder X-ray diffraction (PXRD), photoluminescence properties). The impact of substitutions is significant on the thermal properties, lowering the Tm down to 100 °C for (C4)2Pb(Br0.25Cl0.75)4. The emission properties are slightly tuned in the case of mixed organic cation systems, whereas modifications are more dramatic in the case of mixed halide systems, leading to emission properties through the entire visible region. These results illustrate the great opportunities offered by the congruent melting properties of halide perovskites allowing syntheses in the molten state.

A new G-quadruplex-specific photosensitizer inducing genome instability in cancer cells by triggering oxidative DNA damage and impeding replication fork progression.

Photodynamic therapy (PDT) ideally relies on the administration, selective accumulation and photoactivation of a photosensitizer (PS) into diseased tissues. In this context, we report a new heavy-atom-free fluorescent G-quadruplex (G4) DNA-binding PS, named DBI. We reveal by fluorescence microscopy that DBI preferentially localizes in intraluminal vesicles (ILVs), precursors of exosomes, which are key components of cancer cell proliferation. Moreover, purified exosomal DNA was recognized by a G4-specific antibody, thus highlighting the presence of such G4-forming sequences in the vesicles. Despite the absence of fluorescence signal from DBI in nuclei, light-irradiated DBI-treated cells generated reactive oxygen species (ROS), triggering a 3-fold increase of nuclear G4 foci, slowing fork progression and elevated levels of both DNA base damage, 8-oxoguanine, and double-stranded DNA breaks. Consequently, DBI was found to exert significant phototoxic effects (at nanomolar scale) toward cancer cell lines and tumor organoids. Furthermore, in vivo testing reveals that photoactivation of DBI induces not only G4 formation and DNA damage but also apoptosis in zebrafish, specifically in the area where DBI had accumulated. Collectively, this approach shows significant promise for image-guided PDT.

Synthesis of 1,6/7-(NO2 )2 -Perylenediimide and 1,6/7-(NH2 )2 -Perylenediimide as Regioisomerically Pure Materials.

The use of perylenediimide (PDI) building blocks in materials for organic electronic is of considerable interest. This popular n-type organic semiconductor is tuned by introducing peripheral groups in their ortho and bay positions. Such modifications radically alter their optoelectronic properties. In this article, we describe an efficient method to afford regioisomerically pure 1,6/7-(NO2 )2 - and (NH2 )2 -PDIs employing two key steps: the selective crystallization of 1,6-(NO2 )2 -perylene-3,4,9,10-tetracarboxy tetrabutylester and the nitration of regiopure 1,7-Br2 -PDI with silver nitrite. The optoelectronic properties of the resulting regioisomerically pure dinitro, diamino-PDIs and bisazacoronenediimides (BACDs) are reported and demonstrate the need to separate both regioisomers of such n-type organic semiconductors for their inclusion in advanced optoelectronic devices. For the first time, the two regioisomers of the same PDI starting material are available on the multigram scale, which will stimulate the exploration of regioisomerism/properties relationship for this family of dyes.

Tweaking the Optoelectronic Properties of S-Doped Polycyclic Aromatic Hydrocarbons by Chemical Oxidation.

Peri-thiaxanthenothiaxanthene, an S-doped analog of peri-xanthenoxanthene, is used as a polycyclic aromatic hydrocarbon (PAH) scaffold to tune the molecular semiconductor properties by editing the oxidation state of the S-atoms. Chemical oxidation of peri-thiaxanthenothiaxanthene with H2 O2 led to the relevant sulfoxide and sulfone congeners, whereas electrooxidation gave access to sulfonium-type derivatives forming crystalline mixed valence (MV) complexes. These complexes depicted peculiar molecular and solid-state arrangements with face-to-face π-π stacking organization. Photophysical studies showed a widening of the optical bandgap upon progressive oxidation of the S-atoms, with the bis-sulfone derivative displaying the largest value (E00 =2.99 eV). While peri-thiaxanthenothiaxanthene showed reversible oxidation properties, the sulfoxide and sulfone derivatives mainly showed reductive events, corroborating their n-type properties. Electric measurements of single crystals of the MV complexes exhibited a semiconducting behavior with a remarkably high conductivity at room temperature (10-1 -10-2  S cm-1 and 10-2 -10-3  S cm-1 for the O and S derivatives, respectively), one of the highest reported so far. Finally, the electroluminescence properties of the complexes were tested in light-emitting electrochemical cells (LECs), obtaining the first S-doped mid-emitting PAH-based LECs.

Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction.

We report the experimental reassessment of the widely admitted concerted reduction mechanism for diazonium electroreduction. Ultrafast cyclic voltammetry was exploited to demonstrate the existence of a stepwise pathway, and real-time spectroelectrochemistry experiments allowed visualization of the spectral signature of an evolution product of the phenyldiazenyl radical intermediate. Unambiguous identification of the diazenyl species was achieved by radical trapping followed by X-ray structure resolution. The electrochemical generation of this transient under intermediate energetic conditions calls into question our comprehension of the layer structuration when surface modification is achieved via the diazonium electrografting technique as this azo-containing intermediate could be responsible for the systematic presence of azo bridges in nanometric films.

Site-selected thionated benzothioxanthene chromophores as heavy-atom-free small-molecule photosensitizers for photodynamic therapy.

Photodynamic therapy is a clinically approved anticancer modality that employs a light-activated agent (photosensitizer) to generate cytotoxic reactive oxygen species (ROS). There is therefore a growing interest for developing innovative photosensitizing agents with enhanced phototherapeutic performances. Herein, we report on a rational design synthetic procedure that converts the ultrabright benzothioxanthene imide (BTI) dye into three heavy-atom-free thionated compounds featuring close-to-unit singlet oxygen quantum yields. In contrast to the BTI, these thionated analogs display an almost fully quenched fluorescence emission, in agreement with the formation of highly populated triplet states. Indeed, the sequential thionation on the BTI scaffold induces torsion of its skeleton reducing the singlet-triplet energy gaps and enhancing the spin-orbit coupling. These potential PSs show potent cancer-cell ablation under light irradiation while remaining non-toxic under dark condition owing to a photo-cytotoxic mechanism that we believe simultaneously involves singlet oxygen and superoxide species, which could be both characterized in vitro. Our study demonstrates that this simple site-selected thionated platform is an effective strategy to convert conventional carbonyl-containing fluorophores into phototherapeutic agents for anticancer PDT.

From Zero- to One-Dimensional, Opportunities and Caveats of Hybrid Iodobismuthates for Optoelectronic Applications.

The association of the electron acceptor 4,4'-amino-bipyridinium (AmV2+) dication and BiI3 in an acidic solution affords three organic-inorganic hybrid materials, (AmV)3(BiI6)2 (1), (AmV)2(Bi4I16) (2), and (AmV)BiI5 (3), whose structures are based on isolated BiI63- and Bi4I164- anion clusters in 1 and 2, respectively, and on a one-dimensional (1D) chain of trans-connected corner-sharing octahedra in 3. In contrast with known methylviologen-based hybrids, these compounds are more soluble in polar solvents, allowing thin film formation by spin-coating. (AmV)BiI5 exhibits a broad absorption band in the visible region leading to an optical bandgap of 1.54 eV and shows a PV effect as demonstrated by a significant open-circuit voltage close to 500 mV. The electronic structure of the three compounds has been investigated using first-principles calculations based on density functional theory (DFT). Unexpectedly, despite the trans-connected corner-shared octahedra, for (AmV)BiI5, the valence state shows no coupling along the wire direction, leading to a high effective mass for holes, while in contrast, the strong coupling between Bi 6px orbitals in the same direction at the conduction band minimum suggests excellent electron transport properties. This contributes to the low current output leading to the low efficiency of perovskite solar cells based on (AmV)BiI5. Further insight is provided for trans- and cis-MI5 1D model structures (M = Bi or Pb) based on DFT investigations.

Exciton Coupling in Redox-Active Salen based Self-Assembled Metallacycles.

The incorporation of a redox-active nickel salen complex into supramolecular structures was explored via coordination-driven self-assembly with homobimetallic ruthenium complexes (bridged by oxalato or 5,8-dihydroxy-1,4-naphthoquinato ligands). The self-assembly resulted in the formation of a discrete rectangle using the oxalato complex and either a rectangle or a catenane employing the larger naphthoquinonato complex. The formation of the interlocked self-assembly was determined to be solvent and concentration dependent. The electronic structure and stability of the oxidized metallacycles was probed using electrochemical experiments, UV-Vis-NIR absorption, EPR spectroscopy and DFT calculations, confirming ligand radical formation. Exciton coupling of the intense near-infrared (NIR) ligand radical intervalence charge transfer (IVCT) bands provided further confirmation of the geometric and electronic structures in solution.

Reversible pH-Controlled Catenation of a Benzobisimidazole-Based Tetranuclear Rectangle.

The development of methodologies to control on demand and reversibly supramolecular transformations from self-assembled metalla-structures requires the rational design of architectures able to answer to an applied stimulus. While solvent or concentration changes, light exposure or addition of a chemical have been largely explored to provide these transformations, the case of pH sensitive materials is less described. Herein, we report the first example of a pH-triggered dissociation of a coordination-driven self-assembled interlocked molecular link. It incorporates a pH sensitive benzobisimidazole-based ligand that can be selectively protonated on its bisimidazole moieties. This generates intermolecular electrostatic repulsions that reduces drastically the stability of the interlocked structure, leading to its dissociation without any sign of protonation of the pyridine moieties involved in the coordination bonds. Importantly, the dissociation process is reversible through addition of a base.

Investigation of the K4[Fe(CN)6]-Mediated Mono- and Bis-Palladium-Catalyzed Cyanation of the Benzothioxanthene Core.

The pallado-catalyzed cyanation of benzothioxanthene imide (BTXI) derivatives is explored herein. Once optimized on the monobromo BTXI, mild reaction conditions were successfully applied to the dibromo derivative affording two regioisomers that have been isolated and structurally solved. Additional hydrogen-deuterium exchange experiments were carried out to support a proposed mechanism involving the formation of a five-membered palladacycle intermediate in the bay area. As well as impacting the structural, photo physical and electrochemical properties of the BTXI core, nitrile moieties were successfully used as orthogonal protecting groups, thus opening doors to new design principles.

Exploring the Electronic Properties of Extended Benzofuran-Cyanovinyl Derivatives Obtained from Lignocellulosic and Carbohydrate Platforms Raw Materials.

Two series of linear extended benzofuran derivatives associating cyanovinyl unit and phenyl or furan moieties obtained from benzaldehyde-lignocellulosic (Be series) or furaldehyde -saccharide (Fu series) platforms were prepared in order to investigate their emission and electrochemical properties. For the fluorescence in solution and solid states, contrasting results between the two series were demonstrated. For Be series a net aggregation induced emission effect was observed with high fluorescence quantum yield for the solid state. A [2+2] cycloaddition under irradiation at 350 nm was also revealed for one derivative of Be series. In contrast, for Fu series the fluorescence in solution is higher than in the solid state. The X-ray crystallography studies for the compounds reveal the formation of strong π-π stacking for the derivatives without emissive property in the solid state and the presence of essentially lateral contacts for emissive compounds. Taking advantage of the propensity to develop 2D π-stacking mode for the more extended derivative with a central furan cycle, organic field effect transistors presenting hole mobility have been made.

Synthesis, characterization and use of benzothioxanthene imide based dimers.

The synthesis of benzothioxanthene imide based dimers is reported herein. Subtle chemical modifications were carried out and their impact on the optical and electrochemical properties was investigated for a better structure-property relationship analysis. The icing on the cake was that these new structures were used as light emitting materials for the fabrication and demonstration of the first BTXI-based OLEDs.