David B. Amabilino

Spontaneous resolution, whence and whither: from enantiomorphic solids to chiral liquid crystals, monolayers and macro- and supra-molecular polymers and assemblies

One of the great challenges in stereochemistry is the explanation of why some molecules resolve spontaneously while others do not. In this critical review the recent advances in the creation of chiral systems from achiral and racemic compounds in three-, two- and one-dimensional systems are discussed. There are some groups of molecules in some systems that do tend to display conglomerates, which may suggest that there are enantiophobic and enantiophilic molecules whose assembly is guided by the structural and thermodynamic properties of the systems in question.

Surface Supramolecular Organization of a Terbium(III) Double-Decker Complex on Graphite and its Single Molecule Magnet Behavior

The two-dimensional self-assembly of a terbium(III) double-decker phthalocyanine on highly oriented pyrolitic graphite (HOPG) was studied by atomic force microscopy (AFM), and it was shown that it forms highly regular rectangular two-dimensional nanocrystals on the surface, that are aligned with the graphite symmetry axes, in which the molecules are organized in a rectangular lattice as shown by scanning tunneling microscopy. Molecular dynamics simulations were run in order to model the behavior of a collection of the double-decker complexes on HOPG. The results were in excellent agreement with the experiment, showing that-after diffusion on the graphite surface-the molecules self-assemble into nanoscopic islands which align preferentially along the three main graphite axes. These low dimension assemblies of independent magnetic centers are only one molecule thick (as shown by AFM) and are therefore very interesting nanoscopic magnetic objects, in which all of the molecules are in interaction with the graphite substrate and might therefore be affected by it. The magnetic properties of these self-assembled bar-shaped islands on HOPG were studied by X-ray magnetic circular dichroism, confirming that the compounds maintain their properties as single-molecule magnets when they are in close interaction with the graphite surface.

A Liquid‐Crystalline Single‐Molecule Magnet with Variable Magnetic Properties

This work was supported by the Marie Curie EST FuMaSSEC, EU NoE MAGMANet (515767-2), EMOCIONA (CTQ2006-06333/BQU), Grup de Recerca de Catalunya (2009 SGR-516) and Molecular Nanoscience (CSD2007-00010) and Molchip (MAT2009-13977-C03) projects.

Amino Acid Based Metal−Organic Nanofibers

Long chiral metal-organic nanofibers can be grown using conventional coordination chemistry and biologically derived components in a diffusion controlled growth procedure.

Spontaneous resolution under supramolecular controlAbbreviations. 0D: Zero-dimensional; 1D: One-dimensional; 2D: Two-dimensional; 3D: Three-dimensional; CD: Circular Dichroism; LC: Liquid Crystal ; ML: Monolayer; M: Minus (left-handed) helicity; P: Plus (right-handed) helicity; STM: Scanning Tunnelling Microscopy; UHV: Ultra-high vacuum.

The spontaneous resolution of enantiomers is an intriguing and important phenomenon in a number of research areas. Non-covalent interactions can play a key role in the process which can now be observed not only in crystals, but in liquid crystals, self-assembled monolayers, self-assembled fibres, and supramolecules self-assembled in solution. The evidence gathered in all of these areas is important for explaining the transfer of chirality from molecule to bulk, and in particular the spontaneous resolution of enantiomers.

Probing the Magnetic Properties of Three Interconvertible Redox States of a Single-Molecule Magnet with Magnetic Circular Dichroism Spectroscopy

The hysteresis of magnetization of the anionic, neutral, and cationic forms of a bis(phthalocyaninato)terbium-based complex ([Pc(2)Tb](-/0/+)) have been determined using magnetic circular dichroism (MCD) spectroscopy in frozen dilute solutions at low temperatures (1.5 K) showing that the three oxidation states of the complex exhibit single-molecule magnetic behaviors.

Tuning the Supramolecular Chirality of One- and Two-Dimensional Aggregates with the Number of Stereogenic Centers in the Component Porphyrins

A synthetic strategy was developed for the preparation of porphyrins containing between one and four stereogenic centers, such that their molecular weights vary only as a result of methyl groups which give the chiral forms. The low-dimensional nanoscale aggregates of these compounds reveal the profound effects of this varying molecular chirality on their supramolecular structure and optical activity. The number of stereogenic centers influences significantly the self-assembly and chiral structure of the aggregates of porphyrin molecules described here. A scanning tunneling microscopy study of monolayers on graphite shows that the degree of structural chirality with respect to the surface increases almost linearly with the number of stereogenic centers, and only one handedness is formed in the monolayers, whereas the achiral compound forms a mixture of mirror-image domains at the surface. In solution, four hydrogen bonds induce the formation of an H-aggregate, and circular dichroism measurements and theoretical studies indicate that the compounds self-assemble into helical structures. Both the chirality and stability of the aggregates depend critically on the number of stereocenters. The chiral porphyrin derivatives gelate methylcyclohexane at concentrations dependent on the number and position of chiral groups at the periphery of the aromatic core, reflecting the different aggregation forces of the molecules in solution. Increasing the number of stereogenic centers requires more material to immobilize the solvent, in all likelihood because of the greater solubility of the porphyrins. The vibrational circular dichroism spectra of the gels show that all compounds have a chiral environment around the amide bonds, confirming the helical model proposed by calculations. The morphologies of the xerogels (studied by scanning electron microscopy and scanning force microscopy) are similar, although more fibrous features are present in the molecules with fewer stereogenic centers. Importantly, the presence of only one stereogenic center, bearing a methyl group as the desymmetrizing ligand, in a molecule of considerable molecular weight is enough to induce single-handed chirality in both the one- and two-dimensional supramolecular self-assembled structures.

Shaping Supramolecular Nanofibers with Nanoparticles Forming Complementary Hydrogen Bonds

Functionalized gold nanoparticles with complementary H-bonding groups can control the secondary structure of xerogel fibers formed by a molecular conductor thanks to their incorporation into the nanowires, which show metal-like conductivity once doped without the need for annealing. The picture shows a photograph of the xerogel, TEM images of Au particles in the gel and a single fiber, and an AFM image revealing the texture of the gel.

Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface.

Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

Gemini Imidazolium Amphiphiles for the Synthesis, Stabilization, and Drug Delivery from Gold Nanoparticles

Gold nanoparticles (AuNPs) are considered useful vehicles for medical therapy and diagnosis. Despite the progress made in this field, there is need to find direct, reliable, and versatile synthetic procedures for their preparation as well as new multifunctional coating agents. In this sense, we have explored the use of imidazolium amphiphiles to prepare new AuNPs designed for anion recognition and transport. Thus, in this work we describe (a) the synthesis, by a phase transfer method, of new gold nanoparticles using gemini-type surfactants as ligands based on imidazolium salts, those ligands acting as transfer agents into organic media and also as nanoparticle stabilizers, (b) the examination of their stability in solution, (c) the chemical and physical characterization of the nanoparticles, using a variety of techniques, including UV-visible spectroscopy (UV-vis), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), (d) toxicity data concerning both the imidazolium ligands and the imidazolium coated nanoparticles, (e) the assessment of their molecular recognition ability toward molecules of biological interest, such as anions and carboxylate containing model drugs, such as ibuprofen, (f) the study of their toxicity and those of their coating ligands, as well as their ability for cell internalization, and (g) the study of their ability for delivering anionic pharmaceuticals. The structurally governed triple role of those new gemini-type surfactants is responsible for the preparation, remarkable stability, and delivery properties of these functional AuNPs.