Tuning the slow magnetic relaxation with the substituents in anilate bridged bis(dysprosium) complexes.

Dinuclear lanthanide complexes [((HB(pz)3)2Dy)2(µ-Th2An)] (1Dy) and [((HB(pz)3)2Dy)2(µ-ClCNAn)] (2Dy), based on the hydrotris(pyrazol-1-yl)borate (HBpz3-) scorpionate capping ligand and anilate (An2-) bridging linkers, namely homosubstituted dithiophene- and heterosubstituted chlorocyanoanilate, bearing electron-donating and withdrawing substituents at the 3,6-positions of the benzoquinone core, are reported. 1Dy shows an octacoordinated {N6O2} DyIII ion within a D4h distorted square antiprismatic coordination, an ideal geometry for Single-Molecule Magnet (SMM) behavior, given its oblate nature, whereas in 2Dy the octacoordinated DyIII ion adopts a D2d triangular dodecahedron geometry, while maintaining the same {N6O2} coordination sphere. Both complexes show field-induced single molecule magnet (SMM) behaviour, with tuning of the slow magnetic relaxation as a function of the nature of the substituents at the 3,6-positions of the anilate moiety. A comparison of the Arrhenius fitting parameters for 1Dy and 2Dy supports the hypothesis that square antiprismatic DyIII complexes, as 1Dy, exhibit higher energy barriers. This interpretation is supported by ab initio calculations that also shed light on the crucial role of intermolecular dipolar interactions.

Chiral Spiro-Tetrathiafulvalenes: Synthesis, Chiroptical Properties, Conformational Issues and Charge Transfer Complexes.

Within this work we have investigated spiro-based tetrathiafulvalenes (TTFs) obtained as mixtures of stereoisomers from racemic spiro[5.5]undeca-1,8-dien-3-one. Compared to previously described spiro-TTFs, enantiomeric and diastereoisomeric forms have been here separated by chiral HPLC and fully characterized both experimentally and theoretically. The two types of spiro-based chiral derivatives contain either one (2) or three (1) chiral centres out of each one is spiro-type. Experimental CD, supported by TD-DFT calculations, shows differences in the optical activity between the 1 and 2 and their intermediates. The low optical activity of 2 and 3 (spiro alone chirality) was attributed to the presence of two conformers in the solution (ax and eq) of opposite Cotton effect whereas in the case of 1 and 5 (spiro and stereogenic centres) the spiro chirality seems to be responsible of the Cotton effect in the high energy region whereas the R and S chirality in the low energy region. Racemic and enantiopure forms have been successfully used for the synthesis of charge transfer complexes with tetracyanoquinodimethane (TCNQ) based acceptors.

The Antioxidant Effect of Burdock Extract on the Oxidative Stability of Lard and Goose Fat during Heat Treatment.

Concerns regarding product quality and nutrition are raised due to the effects of high temperatures on frying fats. The aim of this research was to examine the effects of temperature and burdock extract addition in relation to quality parameters for dietary lard and goose fat exposed to heating. In order to monitor quality changes, animal fats and 0.01% additivated fats were heated at different temperatures (110, 130, 150, 170, 190, and 210 °C for 30 min). Thiobarbituric acid-reactive substances test (TBARS), peroxide value (PV), iodine value (IV), acid value (AV), saponification value (SV), total polar compounds (TPoC), total phenolic content (TPC), fatty acid (FA) content, and microscopic examination were established in order to quantify the level of oxidative rancidity. Heating temperature and additivation had a significant (p < 0.001) effect on peroxide value. In all fats, values of thiobarbituric acid-reactive substances significantly (p < 0.001) increased with heating temperature, but values decreased when burdock extract was added in a proportion of 0.01%. Positive correlations were found between AV and PV for lard (r = 0.98; p < 0.001) and goose fat (r = 0.96; p < 0.001). The heating temperature had a significant effect on total MUFAs in both lard and goose fat (mostly in non-additivated fat). Statistical analysis of the data showed that the addition of burdock extract at a concentration of 0.01% significantly (p < 0.01) reduced the installation of oxidation process in alimentary fats heated at different temperatures. Animal fats were well protected from oxidation by burdock extract, which demonstrated its efficacy as an antioxidant; it may be used to monitor the fats oxidation and to estimate their shelf-life stability.

Spin-dependent electrochemistry and electrochemical enantioselective recognition with chiral methylated bis(ethylenedithio)-tetrathiafulvalenes.

Enantio-discrimination and spin-dependent electrochemistry (SDE), as a manifestation of the chirality-induced spin selectivity (CISS) effect, are important phenomena that can be probed by "chiral" electrochemistry. Here, we prepared chiralized surfaces of gold and nickel, to serve as working electrodes, through effective chemisorption of enantiopure dimethyl-bis(ethylenedithio)-tetrathiafulvalene (DM-BEDT-TTF) 1, tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) 2, and their capped silver nanoparticle (AgNPs) aggregate by simple incubation of the metallic substrates. The effective chemisorption was checked by means of ultrahigh vacuum x-ray photoelectron spectroscopy (XPS) and by electro-desorption experiments, i.e., cyclic voltammetry (CV) scans showing a first electro-desorption peak at about -1.0 V. The Au|1 and Au|2 chiral electrodes were successfully used in CV experiments exploiting chiral redox probes. Finally, the hybrid interfaces Ni|enantiopure 1 or 2|AgNPs served as working electrodes in SDE experiments. In particular, the hybrid chiral interfaces Ni|(R)-2|AgNPs and Ni|(S)-2|AgNPs exhibited a significant spin-filtering ability, as a manifestation of the CISS effect, with average spin polarization values of 15%.

Tuning the photophysical and chiroptical properties of [4]helicene-diketopyrrolopyrroles.

Synthesis and functionalization of diketopyrrolo[3,4-c]pyrrole (DPP) derivatives containing chiral groups able to induce a strong chiral perturbation of the DPP core are still a challenging task. We report in this work the straightforward preparation of four bis([4]helicene)-DPP and bis([4]thiahelicene)-DPP dyes upon the condensation of 2-CN-[4](thia)helicene precursors, followed by their N-alkylation by nucleophilic substitution (compounds 9-11) or by a Mitsunobu-type strategy (compound 12). Compound 12, which contains sec-phenylethyl groups attached to the nitrogen atoms, has been obtained as (R,R) and (S,S) enantiomers. The four DPP-helicenes are luminescent in solution, while the N-benzyl (10) and N-sec-phenethyl (12) are emissive in the solid state as well. The chiroptical properties of compound 12 in solution and in the solid state indicate a strong chiral perturbation provided by the α-stereogenic centres, in spite of the stereodynamic nature of the [4]helicene flanking units.

Self-assembly of chiral diketopyrrolopyrrole chromophores giving supramolecular chains in monolayers and twisted microtapes.

Chiral diketopyrrolopyrroles appended with enantiomeric ethyl lactate functions through an ether linkage to the aryl backbone of the chromophore were synthesized via the Mitsunobu reaction. The molecules have good solubility and excellent optical properties, high molar absorption coefficients, and fluorescence quantum yields. Helical aggregates with circular dichroism arising from the supramolecular arrangement are seen in both solution and thin films, and the aggregates also display circularly polarized luminescence (glum  ≈ ±0.1). The molecules assemble to give monolayers on graphite and precipitate from solution forming supramolecular twisted tapes hundreds of microns long.

Chiral Bis(tetrathiafulvalene)-1,2-cyclohexane-diamides.

Chiral bis(TTF) diamides have been obtained in good yields (54-74%) from 1,2-cyclohexane-diamine and the corresponding TTF acyl chlorides. The (R,R)-1 and (S,S)-1 enantiomers have been characterized by circular dichroism and the racemic form by single-crystal X-ray diffraction. The neutral racemic bis(TTF)-diamide shows the formation of a pincer-like framework in the solid state, thanks to the intramolecular S···S interactions. The chemical oxidation in a solution using FeCl3 provides stable oxidized species, while the electrocrystallization experiments provided radical cation salts. In particular, single-crystal resistivity measurements on the racemic donor with AsF6- as a counterion demonstrate semiconductor behavior in this material. The DFT and TD-DFT calculations support the structural and chiroptical features of these new chiral TTF donors.

Chiroptical properties of anionic and neutral nickel(II) bis(dithiolene) complexes based on methyl and dimethyl-dddt ligands.

Racemic and enantiopure nickel(II) bis(dithiolene) anionic and neutral complexes based on the methyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (me-dddt) and dimethyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (dm-dddt) ligands have been experimentally and theoretically investigated with a special focus on their chiroptical properties. According to the time-dependent density-functional theory (TD-DFT) calculations, the strong near-infrared absorption bands typical for such complexes are only weakly active in circular dichroism (CD), and moreover, they have opposite signs for the axial and equatorial conformations, due to the variation of the angle between the transition electric and magnetic dipole moments, thus leading to the mutual cancellation of their contributions and the absence of these bands in the experimental CD spectra. The influence of the number of stereogenic centers and of the oxidation state of the complexes on their chiroptical properties is highlighted. The solid-state structure of the complex (TMA)[Ni(rac-me-dddt)2 ] (TMA = tetramethylammonium), determined by single-crystal X-ray diffraction analysis, shows a rather unusual cis arrangement of the two dithiolene ligands, with the methyl substituents adopting an axial conformation, which is not the most stable one in the gas phase.

Straightforward N-alkylation of diketopyrrolopyrroles through the Mitsunobu reaction with benzyl, α-branched, and chiral alcohols.

The N-alkylation of diketopyrrolopyrroles (DPPs) represents a fundamental step to ensure solubility and further processability. Commonly used nucleophilic substitution in halogenated derivatives is replaced in this work by the Mitsunobu reaction affording unprecedented DPPs with α-branched and chiral chains.

Thiophene-Bipyridine Appended Diketopyrrolopyrrole Ligands and Platinum(II) Complexes.

Straightforward palladium(II) catalyzed direct cross-coupling reaction between decyl, (S)-2-methyl-butyl, and dodecyl N-substituted diketopyrrolopyrrole thiophene (DPPT), including a 3-methoxy-thiophene derivative, and 6-bromo-2,2'-bipyridine afforded a series of mono- and bis-bipyridine substituted DPPT ligands 1-3. Complexation reactions with PtCl2(DMSO)2 provided ortho-metalated platinum(II) complexes 1-Pt and 2-Pt, together with the N^N^O complex 3d-Pt(N^N^O) resulted from the O-Me activation of the intermediary complex 3d-Pt(N^N). The ligand 1b and the mononuclear complexes 1a-Pt and 1b-Pt have been structurally characterized by single crystal X-ray structure, evidencing the establishment of numerous intermolecular π-π interactions in the solid state. Moreover, in the crystal structure of the model complex DMTB-Pt(N^N^O) (DMTB = 3,4-dimethoxy-(2,2'-bipyridine)) the chelating tridentate N^N^O mode is clearly evidenced. The chiral ligand 1b and its mononuclear complex 1b-Pt do not show any CD signal in solution, but they are CD active in the solid state with bisignate bands in the low energy region, opposite in sign between the ligand and the complex, suggesting helical supramolecular arrangement of the dpp chromophore in the solid state. Photophysical investigations demonstrate that all of the ligands are fluorescent with high quantum yields, while the emission is quenched for the complexes, except partially in 3d-Pt(N^N), very likely through an intersystem crossing mechanism promoted by the heavy metal. Density functional theory calculations support the differences observed between the absorption properties of the ligands, ortho- and non-ortho-metalated complexes. The highly fluorescent bipyridine ligands reported herein open the way toward multifunctional transition metal complexes and their use in organic electronics.

Tuning the Organogelating and Spectroscopic Properties of a C3 -Symmetric Pyrene-Based Gelator through Charge Transfer.

Two-component organogels and xerogels based on a C3 -symmetric pyrene-containing gelator have been deeply characterized through a wide range of techniques. Based on the formation of charge transfer complexes, the gelation phenomenon proved to be highly dependent on the nature of the electron poor dopant. This parameter significantly influenced the corresponding gelation domains, the critical gelation concentrations of acceptor dopants, the gel-to-sol transition temperatures, the microstructures formed in the xerogel state and their spectroscopic properties. In particular, titrations and variable-temperature UV-visible absorption spectroscopy demonstrated the key role of donor-acceptor interactions with a remarkable correlation between the phase transition temperatures and the disappearance of the characteristic charge transfer bands. The assignment of these electronic transitions was confirmed through time-dependent density functional theory (TD-DFT) calculations. Eventually, it was shown that the luminescent properties of these materials can be tuned with the temperature, either in intensity or emission wavelength.

In Search of Chiral Molecular Superconductors: κ-[(S,S)-DM-BEDT-TTF]2 ClO4 Revisited.

The relationship between chirality and superconductivity is an intriguing question. The two enantiomeric crystalline radical cation salts κ-[(S,S)-DM-BEDT-TTF]2 ClO4 and κ-[(R,R)-DM-BEDT-TTF]2 ClO4 , showing κ-type arrangement of the organic layers, are investigated in search for superconducting chiral molecular materials following a 1992 report indicating the occurrence of a superconducting transition in the former compound. While the initial interpretation is presently challenged through in-depth temperature and pressure dependent single crystal resistivity measurements combined with band structure calculations, the two chiral conductors show metal like behavior with room temperature conductivities of 10-30 S cm-1 at ambient pressure and stabilization of the metallic state down to the lowest temperatures under moderate pressures. Moreover, their structural and theoretical investigations reveal an original feature, namely the existence of two different κ layers with 1D and 2D electronic dimensionality, respectively, as a consequence of an interlayer charge transfer. The resistivity drop observed for one sample below 1 K and insensitive to magnetic field, possibly results from mixing in-plane and out-of-plane contributions to the measured resistance and suggests current induced charge order melting. This feature contradicts the occurrence of superconductivity in these chiral molecular conductors and leaves open the discovery of the first chiral molecular superconductors.

Main-Group-Based Electro- and Photoactive Chiral Materials.

This Review discusses the structure-property relationships in chiral molecules, macromolecules (polymers), and supramolecules (crystals, liquid crystals, or thin films) containing main-group elements. Chirality is a major property in our world, having a prominent influence on processes in biology, chemistry, and physics. Its impact in optics due to its interaction with electromagnetic waves gave rise to a multitude of effects, such as the Cotton effect and circularly polarized luminescence, making possible applications such as 3D displays and polarized sunglasses. Herein, a particular emphasis will be given to the influence of chirality on the conducting and optical properties of molecules or materials containing frontier heteroelements, particularly boron, silicon, phosphorus, and sulfur. These synergic materials are expected to become game-changers in the field of materials science by bringing new properties into the realm of reality, such as chirality-induced spin-selectivity, circularly polarized luminescence, and electrical magnetochiral anisotropy. This Review should be of interest for chemists and also physicists working in the fields of molecular and supramolecular chemistry, and molecular materials in the broadest sense.

Self-Assembly of Chiral-at-End Diketopyrrolopyrroles: Symmetry Dependent Solution and Film Optical Activity and Photovoltaic Performance.

Chiral thiophene-diketopyrrolopyrrole derivatives have been synthesised to investigate the potential of stereochemistry and symmetry as a means of modulating properties by influencing self-assembly of these purely organic materials. In particular, derivatives of diketopyrrolopyrrole were employed because of their proven interest as dyes, especially for organic solar cells. The natural product myrtenal was used as the source of stereochemistry, introduced through a Kröhnke reaction of a thiophene-bearing pyridinium salt and diketopyrrolopyrroles were prepared through Suzuki coupling with this chiral moiety at one end only as well as at both ends. Absorption spectroscopy and electrochemistry confirmed the potential suitability of the compounds for photovoltaic devices. The nanostructures formed by the compounds have been probed with circular dichroism spectroscopy in solution and in films. It is shown that a chiral C2 symmetric molecule assembles in solution giving a strong circular dichroic signal while as a film this optical activity is nulled, whereas an asymmetric homologue is most optically active as a thin film. The X-ray crystal structure of the asymmetric compound shows a polar order of the molecules that might explain this observation. The lack of optical activity in solution is very likely a result of the high solubility of the compound. The results reaffirm the sensitivity of circular dichroism spectroscopy to inter-chromophore organisation, whereas absorption spectroscopy in the visible region reveals only slight changes to the bands. The differing order in the compounds also affects their performance in bulk heterojunction photovoltaic devices. Atomic force microscopy of the blended thin films with the fullerene derivative usually employed (PC61 BM) showed that smooth and well mixed films were achieved, with the conditions required during spin coating depending greatly on the derivative, because of their differing solubility. The apparently better performance of the symmetrical compound (although with very low efficiency) is probably a result of the alignment of the molecules inferred by the circular dichroism experiments, whereas the asymmetric compound presumably adopts a twisted supramolecular organisation.

Conformational Study and Chiroptical Properties of Chiral Dimethyl-Ethylenedithio-Tetrathiafulvalene (DM-EDT-TTF).

The enantiopure dimethyl-ethylenedithio-tetrathiafulvalene (DM-EDT-TTF) donor exists as biaxial (ax, ax) and biequatorial (eq, eq) conformers in equilibrium. DFT calculations combined with free energy surface (FES) analysis establish that the (ax, ax) form is more stable by ∼0.7 kcal·mol-1 than the (eq, eq) one and that the inter-conversion process involves a sequential conformational change through a boat type (ax, eq) conformer with an activation energy of ∼3 kcal.mol-1. TD-DFT calculations show similar, but opposite in sign, CD bands for the two conformers. A Boltzmann type average of the two CD curves, corresponding to a ratio of three (ax, ax) for one (eq, eq) conformers in equilibrium in solution, provides an excellent agreement with the experimental curve.

Tetrathiafulvalene-[2.2]paracyclophanes: Synthesis, crystal structures, and chiroptical properties.

Two racemic tetrathiafulvalene-[2.2]paracyclophane electron donors EDT-TTF-[2.2]paracyclophane 1 and (COOMe)2 -TTF-[2.2]paracyclophane 2 have been synthesized via the phosphite mediated cross coupling strategy. Chiral HPLC allowed the optical resolution of the (RP ) and (SP ) enantiomers for both compounds. Solid-state structures of (RP )-1 and (rac)-2 have been determined by single crystal X-ray analysis. Intermolecular π-π and S•••S interactions are disclosed in the packing. Single crystal X-ray analysis of (RP )-1 combined with experimental and theoretical circular dichroism spectra allowed the assignment of the absolute configuration of the enantiomers of 1 and 2.

Anion size control of the packing in the metallic versus semiconducting chiral radical cation salts (DM-EDT-TTF)2XF6 (X = P, As, Sb).

Control of the structural type in metallic enantiopure and racemic radical cation salts is achieved through hydrogen bonding interactions between the chiral donor DM-EDT-TTF and the XF6 anions (X = P, As, Sb), determined by the anion size and the chiral information.

Localization versus Delocalization in Chiral Single Component Conductors of Gold Bis(dithiolene) Complexes.

The first examples of chiral single component conductors are reported. Both (S,S) and (R,R) enantiomers of 5,6-dimethyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (dm-dddt) ligand have been used to prepare anionic metal bis(dithiolene) complexes formulated as ([(n-Bu)4N][M(dm-dddt)2] (M = Au, Ni), which are isostructural according to single crystal X-ray analysis. Single crystal transport measurements indicate semiconducting behavior for the anionic radical Ni complexes, with low room temperature conductivity values and high activation energies. Electrocrystallization experiments provided neutral [M(dm-dddt)2] (M = Au, Ni) complexes. The neutral radical gold compounds show intermolecular S···S interactions in the solid state giving rise to layers interconnected through weak C-H···S hydrogen bonds. The most peculiar structural feature concerns a dissymmetry between the two dithiolene moieties, while the nickel counterpart is symmetric. Single crystal resistivity measurements show thermally activated behavior for the open-shell gold complexes, with room temperature conductivity values of 0.02-0.04 S·cm(-1) and activation energies strongly influenced by hydrostatic pressure. A thorough theoretical study on nickel anion radical and gold neutral radical bis(dithiolene) complexes applied to the chiral complexes [M(dm-dddt)2] (M = Au, Ni(-)) and to a series of previously reported compounds addressed the issue of symmetry versus asymmetry from an electronic coupling perspective between the two dithiolene ligands. It results that neutral gold complexes with dithiolene ligands without extended delocalization are Class II mixed-valent compounds in the Robin and Day classification, presenting an inherent tendency toward asymmetric structures, which can be however modulated by the intermolecular organization in the solid state.

Covalent non-fused tetrathiafulvalene-acceptor systems.

Covalent donor-acceptor (D-A) systems have significantly contributed to the development of many organic materials and to molecular electronics. Tetrathiafulvalene (TTF) represents one of the most widely studied donor precursors and has been incorporated into the structure of many D-A derivatives with the objective of obtaining redox control and modulation of the intramolecular charge transfer (ICT), in order to address switchable emissive systems and to take advantage of its propensity to form regular stacks in the solid state. In this review, we focus on the main families of non-fused TTF-acceptors, which are classified according to the nature of the acceptor: nitrogen-containing heterocycles, BODIPY, perylenes and electron poor unsaturated hydrocarbons, as well as radical acceptors. We describe herein the most representative members of each family with a brief mention of their synthesis and a special focus on their D-A characteristics. Special attention is given to ICT and its modulation, fluorescence quenching and switching, photoconductivity, bistability and spin distribution by discussing and comparing spectroscopic and electrochemical features, photophysical properties, solid-state properties and theoretical calculations.

Triggering Gel Formation and Luminescence through Donor-Acceptor Interactions in a C3 -Symmetric Tris(pyrene) System.

Straightforward modulation of the gelation, absorption and luminescent properties of a tris(pyrene) organogelator containing a C3 -symmetric benzene-1,3,5-tricarboxamide central unit functionalized by three 3,3'-diamino-2,2'-bipyridine fragments is achieved through donor-acceptor interactions in the presence of tetracyanoquinodimethane.