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.

Additional Insights into the Design of Cr(III) Phosphorescent Emitters Using 6-Membered Chelate Ring Bis(imidazolyl) Didentate Ligands.

The interest in Cr(III) complexes has been renewed over the past decades for building practical guidelines in the design of efficient earth-abundant phosphorescent near-infrared emitters. In that context, we report the first family of homoleptic tri(didentate) Cr(III) complexes [CrL3]3+ based on polyaromatic ligands inducing 6-membered chelate rings, namely, the bis(1-methylimidazol-2-yl)ketone (L = bik), bis(1-methylimidazol-2-yl)methane (L = bim), and bis(1-methylimidazol-2-yl)ethane (L = bie) ligands. The programmed close-to-perfect octahedral microsymmetry of {CrIIIN6} chromophores found in [Cr(bik)3](OTf)3 (1), [Cr(bim)3](OTf)3 (2), and [Cr(bie)3](BF4)3 (3) ensures a ligand-field strength large enough to induce intense and long-lived Cr-based phosphorescence. Impressive excited-state lifetimes (5.0-8.2 ms) were obtained at low temperatures for the [Cr(L)3]3+ series. Additionally, the photoluminescent quantum yield climbs to 0.8% for compound 1 in deaerated solutions. Moreover, the photophysical features of the three homoleptic complexes are barely influenced by the presence of dioxygen presumably because of the poor overlap between the Cr-based phosphorescence spectra (ca. 14100 cm-1) and the 1Σg+ ← 3Σg- transition in the absorption spectrum of dioxygen (13100 cm-1). The multiredox electrochemical pattern of 1 is evidenced by cyclic voltammetry as well as its strong photooxidant behavior. The pH sensitivity of 2 and 3 luminescence is discussed, along with the reactivity of their ß-diketiminate derivatives.

Seeking Brightness in Molecular Erbium-Based Light Upconversion.

Whereas dye-sensitized lanthanide-doped nanoparticles represent an unquestionable advance for pushing linear near-infrared (NIR) to visible-light upconversion within the frame of applications, analogous improvements are difficult to mimic for related but intramolecular processes induced at the molecular level in coordination complexes. Major difficulties arise from the cationic nature of the target cyanine-containing sensitizers (S), which drastically limits their thermodynamic affinities for catching the lanthanide activators (A) required for performing linear light upconversion. In this context, the rare previous design of stable dye-containing molecular SA light-upconverters required large S···A distances at the cost of the operation of only poorly efficient intramolecular S → A energy transfers and global sensitization. With the synthesis of the compact ligand [L2]+, we exploit here the benefit of using a single sulfur connector between the dye and the binding unit for counterbalancing the drastic electrostatic penalty which is expected to prevent metal complexation. Quantitative amounts of nine-coordinate [L2Er(hfac)3]+ molecular adducts could be finally prepared in solution at millimolar concentrations, while the S···A distance has been reduced by 40% to reach circa 0.7 nm. Detailed photophysical studies demonstrate the operation of a three times improved energy transfer upconversion (ETU) mechanism for molecular [L2Er(hfac)3]+ in acetonitrile at room temperature, thanks to the boosted heavy atom effect operating in the close cyanine/Er pair. NIR excitation at 801 nm can thus be upconverted into visible light (525-545 nm) with an unprecedented brightness of Bup(801 nm) = 2.0(1) × 10-3 M-1·cm-1 for a molecular lanthanide complex.

The Atypical Hysteresis of [Fe(C6 F5 Tp)2 ]: Overlay of Spin-Crossovers and Symmetry-Breaking Phase Transition.

The [FeII (C6 F5 Tp)2 ] spin-crossover complex is an atypical molecular switch, which can be converted upon annealing between two archetypal spin-crossover behaviours: from an extremely gradual spin-crossover to a broad hysteretic spin-transition (of ca. 65 K). The hysteresis shows an uncommon "rounded shape" that is reproducible upon cycling temperature. In depth structural studies reveal a first crystal phase transition, which occurs upon melting and recrystallizing at high temperature. This first irreversible transition is associated with a radical change in the crystal packing. More importantly, the "rounded and broad" hysteretic transition is shown to occur in a non-cooperative SCO system and is associated with the occurrence of a symmetry-breaking phase transition that appears when roughly ca. 50 % of the SCO complexes are switched.

Pressure-Induced Conversion of a Paramagnetic FeCo Complex into a Molecular Magnetic Switch with Tuneable Hysteresis.

A key challenge in the design of magnetic molecular switches is to obtain bistability at room temperature. Here, we show that application of moderate pressure makes it possible to convert a paramagnetic FeIII 2 CoII 2 square complex into a molecular switch exhibiting a full dia- to paramagnetic transition: FeII CoIII ⇔ FeIII CoII . Moreover, the complex follows a rare behavior: the higher the pressure, the broader the magnetic hysteresis. Thus, the application of an adequate pressure allows inducing a magnetic bistability at room temperature with predictable hysteresis width. The structural studies at different pressures suggest that the pressure-enhanced bistability is due to the strengthening of intermolecular interactions upon pressure increase. An original microscopic Ising-like model including pressure effects is developed to simulate this unprecedented behavior. Overall, this study shows that FeCo complexes could be very sensitive piezo switches with potential use as sensors.

Electrospray ionization: an efficient approach to deposit polymetallic molecular switches onto gold surfaces.

Electrospray ionization (EI) deposition is proven efficient in obtaining monolayers of a polymetallic charge transfer complex on gold surfaces. The molecule's integrity is monitored by using PM-IRRAS and XPS. This approach broadens the perspective of molecular magnetic switch deposition, which is currently dominated by the thermal evaporation of monometallic spin crossover (SCO) complexes.

Electron Transfer in the Cs⊂{Mn4 Fe4 } Cubic Switch: A Soluble Molecular Model of the MnFe Prussian-Blue Analogues.

A mixed-valence {MnII 3 MnIII FeII 2 FeIII 2 } cyanide-bridged molecular cube hosting a caesium cation, Cs⊂{Mn4 Fe4 }, was synthesized and structurally characterized by X-ray diffraction. Cyclic-voltammetry measurements show that its electronic state can be switched between five different redox states, which results in a remarkable electrochromic effect. Magnetic measurements on fresh samples point to the occurrence of a spin-state change near room temperature, which could be ascribed to a metal-to-metal electron transfer converting the {FeII -CN-MnIII } pair into a {FeIII -CN-MnII } pair. This feature was only previously observed in the polymeric MnFe Prussian-blue analogues (PBAs). Moreover, this novel switchable molecule proved to be soluble and stable in organic solvents, paving the way for its integration into advanced materials.

Direct Observation of Charge Transfer and Magnetism in Fe4Co4 Cyanide-Bridged Molecular Cubes.

We have studied the zero-dimensional cubane molecular correspondent of a Prussian blue analogue Cs-Fe4Co4 at low temperature and high magnetic field by means of L-edge X-ray absorption spectroscopy and X-ray magnetic circular dichroism. We probe the magnetic and electronic structures of Fe and Co separately upon light irradiation, which allows us to observe directly the electron transfer coupled to a spin transition phenomenon within the molecular cubes and to investigate the nature of the metastable photoexcited state. The magnetic moments in the photoexcited state are found to be M = 1.3µB ( Mspin = 0.59µB with large orbital moment, Morbit = 0.74µB) for low-spin FeIII and M = 1.5µB ( Mspin = 1.08µB with orbital moment, Morbit = 0.41µB) for high-spin CoII at 2 K and 6.8 T. From our results, we evidence that a strong antiferromagnetic coupling between the metal ions can be ruled out.

Antibody recognition in multiple sclerosis and Rett syndrome using a collection of linear and cyclic N-glucosylated antigenic probes.

Antibody detection in autoimmune disorders, such as multiple sclerosis (MS) and Rett syndrome (RTT) can be achieved more efficiently using synthetic peptides. The previously developed synthetic antigenic probe CSF114(Glc), a type I' ß-turn N-glucosylated peptide structure, is able to recognize antibodies in MS and RTT patients' sera as a sign of immune system derangement. We report herein the design, synthesis, conformational analysis, and immunological evaluation of a collection of glycopeptide analogs of CSF114(Glc) to characterize the specific role of secondary structures in MS and RTT antibody recognition. Therefore, we synthesized a series of linear and cyclic short glucosylated sequences, mimicking different ß-turn conformations, which were evaluated in inhibition enzyme-linked immunosorbent assays (ELISA). Calculated IC50 ranking analysis allowed the selection of the candidate octapeptide containing two (S)-2-amino-4-pentynoic acid (L-Pra) residues Ac-Pra-RRN(Glc)GHT-Pra-NH2 , with an IC50 in the nanomolar range. This peptide was adequately modified for solid-phase ELISA (SP-ELISA) and surface plasmon resonance (SPR) experiments. Pra-RRN(Glc)GHT-Pra-NH2 peptide was modified with an alkyl chain linked to the N-terminus, favoring immobilization on solid phase in SP-ELISA and differentiating IgG antibody recognition between patients and healthy blood donors with a high specificity. However, this peptide displayed a loss in IgM specificity and sensitivity. Moreover, an analog was obtained after modification of the octapeptide candidate Ac-Pra-RRN(Glc)GHT-Pra-NH2 to favor immobilization on SPR sensor chips. SPR technology allowed us to determine its affinity (KD = 16.4 nM), 2.3 times lower than the affinity of the original glucopeptide CSF114(Glc) (KD = 7.1 nM).