An aperiodic chiral tiling by topological molecular self-assembly.

Studying the self-assembly of chiral molecules in two dimensions offers insights into the fundamentals of crystallization. Using scanning tunneling microscopy, we examine an uncommon aggregation of polyaromatic chiral molecules on a silver surface. Dense packing is achieved through a chiral triangular tiling of triads, with N and N ± 1 molecules at the edges.

Hierarchical chirality observed from chiral supramolecular assembling of racemic and enantiopure helicene derivatives on silica nanohelix surfaces.

Cast films of racemic helicene derivatives adsorbed onto the surface of nanometric silica helices with controlled handedness exhibited distinct CD signals, whereas no CD signal was observed in the absence of silica nanohelices. These CD signals originate from the helical supramolecular assemblies formed by the racemic mixture of helicenes, with no evidence of enantiospecific adsorption. Interestingly, when enantiomerically pure forms of these helicenes were drop-cast onto the silica helices, different CD spectra were observed depending on the combination of the helicenes' handedness with that of the silica nanohelices.

Enantio-Recognition and Charge Transfer Complex Formation Involving Tetrathiafulvalene-Appended Chiral 1,2-Cyclohexane-Diamine: An Integrated Experimental and Theoretical Study.

In this work, we exploit the electronic features of tetrathiafulvalene (TTF) as a backbone in synthesizing chiral derivatives. The aim is to make use of TTF's well-known and unique redox and semiconducting properties in the fields of enantio-selective recognition and chiral charge transfer (CT) complex preparation, with the ultimate objective of obtaining devices with various potential applications, ranging from plasmonics to quantum computing. In particular, both cyclohexane-bis (TTF-amide)-based enantiomers 1-(S,S) and 1-(R,R), stable under an oxidation regime, have been selected, and under these conditions, the electrochemical enantiospecific response of the four possible systems, coming from the combination with L- and D-tartaric acid, respectively, was tested.

Thiophenyl Anilato-Based NIR-Emitting Lanthanide (Ln = Er, Yb) Dinuclear Complexes.

By combining Er and Yb ions with 3,6-dithiophene-anilate (ThAn) and scorpionate hydrotris(pyrazol-1-yl)borate (HBpz) ligands new luminescent dinuclear complexes are obtained. The two materials formulated as [((HB(pz))Yb)(μ-thAn)]·4DCM·1.3HO and [((HB(pz))Er)(μ-thAn)]·4DCM·1.

Enantiomorphic single component conducting nickel(II) and platinum(II) bis(diethyl-dddt) crystalline complexes.

Monoanionic and neutral nickel(II) and platinum(II) bis(dithiolene) complexes based on the 5,6-diethyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (de-dddt) chiral ligand have been prepared in racemic and enantiopure forms. Neutral closed-shell species have been generated from monoanionic precursors upon electrocrystallization. The racemic anionic (TBA)[Ni(,-de-dddt)(,-de-dddt)] complex crystallized in the centrosymmetric space group 2/, while the neutral complexes crystallized in the enantiomorphic tetragonal space group 422 or 422.

A highly conducting tetrathiafulvalene-tetracarboxylate based dysprosium(iii) 2D metal-organic framework with single molecule magnet behaviour.

The synthesis and whole characterization by a multitechnique approach of an unprecedented dysprosium(iii) 2D metal organic framework (MOF), involving the redox-active tetrathiafulvalene (TTF)-based linker TTF-tetracarboxylate (TTF-TC), are herein reported. The single-crystal X-ray structure, formulated as [Dy(TTF-TC)(HO)]·21HO (1), reveals a complex 2D topology, with hexanuclear Dy clusters as secondary building units (SBUs) interconnected by five linkers, stacked almost parallel in each layer and eclipsed along the [111] direction, leading to the formation of 1D channels filled by water molecules. The mixed valence of the TTF units is confirmed by both bond distance analysis, Raman microscopy and diffuse reflectance spectroscopy, and further supported by band structure calculations, which also predict activated conductivity for this material.

Slow magnetic relaxation in a heteroleptic anilate-based Dy metal-organic framework.

Novel heteroleptic anilate-based lanthanide MOFs (Ln = Tb, Dy, Ho) have been obtained under hydrothermal conditions by the ancillary ligand synthetic strategy. These structurally isomorphous species contain octacoordinated Ln ions with coordination polyhedra approaching an ideal symmetry, best described by a distorted biaugmented trigonal prismatic geometry. In the whole series, only the Dy-MOF exhibits SMM behaviour.

Evolution of the ionisation energy with the stepwise growth of chiral clusters of [4]helicene.

Polycyclic aromatic hydrocarbons (PAHs) are widely established as ubiquitous in the interstellar medium (ISM), but considering their prevalence in harsh vacuum environments, the role of ionisation in the formation of PAH clusters is poorly understood, particularly if a chirality-dependent aggregation route is considered. Here we report on photoelectron spectroscopy experiments on [4]helicene clusters performed with a vacuum ultraviolet synchrotron beamline. Aggregates (up to the heptamer) of [4]helicene, the smallest PAH with helical chirality, were produced and investigated with a combined experimental and theoretical approach using several state-of-the-art quantum-chemical methodologies.

Helicene Appended Benzothiadiazoles as Chiral Emitters.

A homologous series of 4,7-bis(aryl) substituted benzothiadiazole (BTD) compounds, containing the helicenic derivatives bis([4]helicene), bis([5]helicene) and bis([6]helicene), have been prepared upon a double Suzuki coupling between 3,6-bis(pinacolyl-borane)-BTD and the corresponding bromo-aryl precursors. The single crystal X-ray structure of the bis([4]helicene) compound shows the existence of both helicities (M) and (P) on the same molecule. All the compounds of the series are highly emissive in solution, with quantum yields of the emission ranging from 50 to 91 %.

Six-coordinated nickel(II) complexes with benzothiadiazole Schiff-base ligands: synthesis, crystal structure, magnetic and HFEPR study.

Two new nickel(II) complexes, namely Ni(L) (1) and Ni(L)·CHCl(2) were obtained by reacting nickel(II) acetate tetrahydrate with the benzothiadiazole Schiff base ligands HL = 2-[4-(2,1,3-benzothiadiazole)imino]methyl-phenol or HL = 2-[(2,1,3-benzothiadiazol-4-ylimino)methyl]-6-methoxyphenol in the presence of EtN. The tridentate NNO chelate ligands induce a distorted octahedral environment around the nickel(II) ions. Single crystal X-ray diffraction analysis reveals elongated Ni-N bonds with the nitrogen atom of the benzothiadiazole ring in both complexes.

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

Dinuclear lanthanide complexes [((HB(pz))Dy)(μ-ThAn)] (1Dy) and [((HB(pz))Dy)(μ-ClCNAn)] (2Dy), based on the hydrotris(pyrazol-1-yl)borate (HBpz) scorpionate capping ligand and anilate (An) 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 {NO} Dy ion within a distorted square antiprismatic coordination, an ideal geometry for Single-Molecule Magnet (SMM) behavior, given its oblate nature, whereas in 2Dy the octacoordinated Dy ion adopts a triangular dodecahedron geometry, while maintaining the same {NO} 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.

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.

Hybrid mesoporous electrodes evidence CISS effect on water oxidation.

Controlling product selectivity is essential for improving the efficiency of multi-product reactions. Electrochemical water oxidation is a reaction of main importance in different applications, e.g.

A redox active rod coordination polymer from tetrakis(4-carboxylic acid biphenyl)tetrathiafulvalene.

An enlarged version of the ubiquitous tetrathiafulvalene-tetrabenzoic acid is described, with 4,4'-biphenyl moieties as spacers between the coordination moieties and the electroactive core. The obtained rectangular ligand has a 14 × 22 Å size and is combined with Zn(II) under solvothermal conditions to yield a coordination polymer endowed with large cavities of . 15 × 11 Å/10 × 10 Å.

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.

Comparing Electrical Magnetochiral Anisotropy and Chirality-Induced Spin Selectivity.

The combination of chirality and magnetism has steadily grown over the past decennia into an area of intense research that evolves around two distinct manifestations and in two nonoverlapping communities: electrical magnetochiral anisotropy (eMChA) and chirality-induced spin-selectivity (CISS). Here, we discuss the similarities and differences of these two effects. Whereas the original CISS reports suggest an intimate relation with eMChA, magnetoresistance (MR) results on two-terminal chiral devices attributed to CISS have symmetry properties that are different from those of eMChA.

Terbium and Europium Chlorocyananilate-Based 2D Coordination Polymers.

Two-dimensional layered coordination polymers based on the hetero-substituted 3-chloro-6-cyano-2,5-dihydroxybenzoquinone ligands, hereafter ClCNAn anilate, and Ln ions (Tb and Eu) are reported. Compounds and , formulated as Ln(ClCNAn)(DMSO) (Ln = Tb, ; Eu, ), and their related intermediates and , formulated as Ln(ClCNAn)(HO)·yHO (x + y likely = 12, Ln = Tb, ; and Eu, ), were prepared by a conventional one-pot reaction (the latter) and recrystallized from DMSO solvent (the former). Polyhydrated intermediates and show very similar XRPD patterns, while, despite their common stoichiometry, and are not isostructural.

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.

Highly Stereospecific On-Surface Dimerization into Bishelicenes: Topochemical Ullmann Coupling of Bromohelicene on Au(111).

The on-surface dimerization into bis(hexahelicene) on a gold(111) surface has been studied by means of scanning tunneling microscopy and time-of-flight secondary mass spectrometry. C-C Ullmann coupling of (rac)-2-bromo-hexahelicene leads to formation of the (M,M)- and (P,P)-diastereomers of 2,2'-bis(hexahelicene), whilst formation of the (M,P)-diastereomer is not observed. Upon cooling, the bis(hexahelicene) aggregates into an ordered two-dimensional lattice with partly randomly distributed enantiomers.

Bis(Vinylenedithio)-Tetrathiafulvalene-Based Coordination Networks.

Novel coordination polymers embedding electroactive moieties present a high interest in the development of porous conducting materials. While tetrathiafulvalene (TTF) based metal-organic frameworks were reported to yield through-space conducting frameworks, the use of S-enriched scaffolds remains elusive in this field. Herein is reported the employment of bis(vinylenedithio)-tetrathiafulvalene (BVDT-TTF) functionalized with pyridine coordinating moieties in coordination polymers.

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 (,)- and (,)- 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 SS interactions.

Dielectric magnetochiral anisotropy.

The combination of chirality and magnetism has steadily grown over the last decennia into an area of intense research. Magnetochiral anisotropy, chirality-induced spin-selectivity and helimagnetism are the most prominent phenomena resulting from this combination, touching different systems like topological (semi-)metals and insulators, quantum magnets, type II multiferroics and enantio-selective synthesis. As an extension to this area, we argue, based on symmetry arguments, that magnetochiral anisotropy will manifest itself in the displacement current in chiral dielectrics in a magnetic field.

Enhancement of electrocatalytic oxygen evolution by chiral molecular functionalization of hybrid 2D electrodes.

A sustainable future requires highly efficient energy conversion and storage processes, where electrocatalysis plays a crucial role. The activity of an electrocatalyst is governed by the binding energy towards the reaction intermediates, while the scaling relationships prevent the improvement of a catalytic system over its volcano-plot limits. To overcome these limitations, unconventional methods that are not fully determined by the surface binding energy can be helpful.

Field-induced mononuclear cobalt(II) single-molecule magnet (SMM) based on a benzothiadiazole--vanillin ligand.

A unique π-conjugated benzothiadiazole--vanillin ligand (HL), characterized by single crystal X-ray diffraction and DFT calculations, has been prepared by condensation between 4-amino-benzothiadiazole (BTD) and -vanillin. Its reaction with cobalt(II) acetate afforded the complex of formula [CoL]·CHCl (1), for which the coordination environment of the cobalt centre is a distorted octahedron and the ligand acts as a monoanionic tridentate chelate in its phenolate form. Intermolecular π-π stacking interactions between the π-conjugated BTD units provide an antiferromagnetic coupling pathway, as indicated by the analysis of the dc magnetic measurements of a crystalline sample of the complex and supported by DFT type calculations.