Self-assembled dimers with supramolecular chirality

The possibilities to form dimeric capsules with supramolecular chirality from tetraurea calix[4]arenes composed of two different phenolic urea units are discussed in general and demonstrated experimentally for various selected examples.     

Amplification of chirality in dynamic supramolecular aggregates

The quest to understand the origin of chirality in biological systems has evoked an intense search for nonlinear effects in catalysis and pathways to amplify slight enantiomeric excesses in racemates to give optically pure molecules. The amplification of chirality in polymeric systems as a result of cooperative processes has been intensely investigated. Ten years ago, this effect was shown for the first time in noncovalent dynamic supramolecular systems. Since then, it has become clear that a subtle interplay of noncovalent interactions such as hydrogen-bonding, pi-pi stacking, and hydrophobic interactions is also sufficient to observe amplification of chirality in small molecules. Here we summarize the results obtained over the past decade and the general guidelines we can deduce from them. Predicting amplification of chirality is still impossible, but it appears to be a balance between different types of interactions, the formation of an intrinsically chiral object, and cooperative aggregation processes.     

Versatile switching in substrate topicity: supramolecular chirality induction in di- and trinuclear host complexes

Supramolecular chirality effects have been achieved both for ditopic and monotopic substrates by using a programmable bis-salphen scaffold that incorporates either two or three Zn nuclei. The dinuclear host shows preferential chirogenesis in the presence of ditopic systems, whereas effective chirality transfer to the trinuclear complex is realized through monotopic binding. The mode of binding in the trinuclear host has been investigated through X-ray crystallography, CD measurements, UV/Vis spectroscopy, and DFT analysis. The bis-salphen scaffold holds promise for the development of substrate-specific host systems useful for determination of the absolute configuration of various types of organic molecules.     

Accessing lipophilic ligands in dendrimer-based amphiphilic supramolecular assemblies for protein-induced disassembly

Supramolecular nanoassemblies that respond to the presence of proteins are of great interest, as aberrations in protein concentrations represent the primary imbalances found in a diseased state. We present here a molecular design, syntheses, and study of facially amphiphilic dendrimers that respond to the presence of the protein, immunoglobulin G. It is of particular interest that the ligand functionality, utilized for causing the binding-induced disassembly, be lipophilic. Demonstration of binding with lipophilic ligands greatly expands the repertoire of binding-induced disassembly, since this covers a rather large class of ligand moieties designed for proteins and these provide specific insights into the mechanistic pathways that are available for the binding-induced disassembly process. Here, we describe the details of the binding induced disassembly, including the change in size of the assembly in response to proteins, concurrent release of noncovalently encapsulated guest molecules, and the specificity of the disassembly process.     

Aggregation and supramolecular chirality of achiral amphiphilic metalloporphyrins

Metalloporphyrin derivatives with three hydrophobic dodecyl chains and a hydrophilic ester or carboxylic acid substituent were designed in order to clarify the effect of the central metal ions on the aggregation as well as the supramolecular chirality in the Langmuir-Schaefer films. All the metalloporphyrins showed good spreading behavior on water surface and can be transferred onto solid substrates. The transferred films were characterized by a variety of methods including UV-visible spectroscopy, circular dichroism (CD) spectroscopy, FTIR spectroscopy, atomic force microscopy (AFM) and scanning electron microscope (SEM) measurements. It has been found that the copper derivative forms J-aggregates as well as H-aggregates in the film. Moreover, the film showed strong CD signals. Change from the ester substitution to carboxylic acid caused the decrease of the supramolecular chirality. On the contrary, the zinc derivative showed only a negligible CD signal although the corresponding free base could assemble into a chiral assembly. A possible mechanism for the subtle relationship between supramolecular chirality and molecular structures has been proposed.     

Photoinduced supramolecular chirality in amorphous azobenzene polymer films

Supramolecular chirality was optically induced in amorphous and achiral azobenzene polymer films by irradiation of a laser beam with elliptical polarization. The chirality resulted from helical orientation of azobenzene chromophores by a combined process of circular and linear polarization. The helix-handedness could be controlled by incident light-handedness.     

Non-covalent dendrimer-based liquid crystalline complexes: Synthesis and characterization

The synthesis and structural characterization of dendritic macromolecules based on 3,5-dihydroxybenzoic acid are described. The molecular structures and purity of all new compounds were confirmed by ¹H NMR, ¹³C NMR spectroscopy and elemental analysis. The dendritic non-covalent liquid crystalline complexes were prepared through the formation of hydrogen bonds between different generation of dendritic acids (proton donor) and stilbazole derivative containing bipyridyl units (proton acceptor). We found that, the hydrogen-bonded dendritic liquid crystals supramolecules (G1-2py, G2-2py and G3-2py) exhibits nematic and semectic phase. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) were used for investigation of the liquid crystalline properties of the hydrogen-bonded dendritic supramolecular complexes.     

Kinetic control of the supramolecular chirality of porphyrin J-aggregates

The aggregation of achiral sulfonatophenyl- and phenyl-meso-substituted diprotonated porphyrins to chiral J-aggregates is a hierarchical noncovalent polymerization process preceded by a critical nucleation stage. This allows significant enantiomeric excesses by the formation of a few primary nuclei and the control of their growth by the effect that flows (imperfect mixing) have on the secondary nucleation of the J-aggregate particles. In addition, the results strongly suggest that when only one species of aggregate predominates, the CD signals of the three excitonic bands in the visible region (around 420, 490, and 700 nm) show the same sign. Thus, differences on their relative sign would be due to the presence of different species.     

Amplification of chirality in benzene tricarboxamide helical supramolecular polymers

The chirality of benzene tricarboxamides is expressed and amplified into the helicity of self-assembled columnar aggregates according to 'sergeants and soldiers' and 'majority rules' principles; the strength of the amplification is analysed quantitatively and the effect of the number of chiral groups in the sergeants is studied.     

Highly fluorescent supramolecular gels with chirality transcription through hydrogen bonding

A highly fluorescent organogel with transparency was formed through a hydrogen (H)-bonding interaction between a non-fluorescent and achiral 2-(3',5'-bis-trifluoromethyl-biphenyl-4-yl)-3-(4-pyridin-4-yl-phenyl)-acrylonitrile (CN-TFMBPPE) monomer and chiral sergeant l-tartaric acid (TA) (or d-TA), with gel formation being accompanied by a drastic fluorescence enhancement as well as chirality induction.     

Quantitative chirality/enantioselectivity relations in large random supramolecular structures

We study the relationship between shape and enantioselectivity, employing quantitative geometric chirality measurements. The model we use comprises of the boundary surfaces of two-dimensional (2D) chiral, large, random selectors (diffusion limited aggregates), interacting with homologous series of small 2D-chiral S-shaped probes (the selectands). We show how the enantioselectivity of the selectors depends on the chirality of the selectands and report the following findings: I) The enantioselectivity of a chiral selector can switch preference from the "right" to the "left" enantiomer within a homologous series of selectands. II) At this switch point the chiral selector is functionally achiral. III) Within a homologous series of chiral selectands, there is a "resonance of recognition", namely, the classical key-lock concept is replaced by a picture of various degrees of recognition. IV) The degree of enantioselectivity and the switch in handedness preference are the outcome of a complex interplay between the details of the specific geometry of the selector and the selectand, and the global shape parameter of chirality measure. V) It is shown that isochiral selectands, namely selectands of the same chirality value, may be recognized differently by a chiral selector. VI) It is proposed that a more realistic way to treat the issue of minimal points needed for chiral interaction is resolution based. VII) It is shown how to attach handedness to purely random objects.     

Electron-induced switching of the supramolecular chirality of optically active polythiophene aggregates

A chiral regioregular polythiophene (PT), poly[3-[4-((R)-4-ethyl-2-oxazolin-2-yl)phenyl]thiophene] (poly-1), forms chiral aggregates which exhibit a unique induced circular dichroism (ICD) in the pi-pi transition region derived from the supramolecular chirality in the presence of various poor solvents or metal salts in chloroform. We report here that the chirality of such supramolecular aggregates can be switched ("on" and "off") through electron transfer. We have found that upon the addition of copper(II) trifluoromethanesulfonate [Cu(OTf)(2)] to the chiral aggregates of poly-1 in a chloroform-acetonitrile mixture, the ICD disappears because of the oxidative doping of the poly-1 main chain, while a further addition of amines such as triethylenetetramine (TETA) induces undoping of the poly-1 which results in the reappearance of the ICDs. Therefore, the supramolecular chirality of the poly-1 assemblies was reversibly controlled by the addition or removal of an electron from the poly-1 main chain. This may be the first example of a reversible supramolecular chirality switch on chiral PT aggregates. We investigated the mechanism of the chirality switch through the doping and undoping process on the polymer main chain by means of absorption and CD spectroscopies, ESR, cyclic voltammetry, X-ray diffraction, and AFM measurements.     

Electrospinning of supramolecular polymer complexes

Supramolecular polymer complexes with small molecules are self-assembled through non-covalent interactions and have been proposed for a wide variety of applications in materials science and nanoscience.Our research group has recently shown the possibility of forming highly ordered nanofibers of supramolecular complexes in their thermodynamically stable state using the electrospinning technique.The ultrafast solvent evaporation rate of electrospinning made possible the in-depth characterization of complexes that had never been prepared in their pure state before because of kinetic issues associated with their formation by conventional approaches.The improved understanding of the formation mechanism allowed us to extend the concept to other techniques featuring a fast solvent evaporation rate,such as electrospray and spin-coating.In this article,we review our most significant contributions in this research field.     

Amplification of chirality in helical supramolecular polymers beyond the long-chain limit

The optical activity of helical homopolymers devoid of chiral centers increases drastically when a small amount of homochiral monomers is incorporated into them. We study this so-called sergeants-and-soldiers effect of chirality amplification in solutions of helical supramolecular polymers with a theoretical model that bears a strong resemblance to a one-dimensional, two-component Ising model. In the limit of very long self-assembled helical polymers, the strength of the sergeants-and-soldiers effect depends strongly on the free energy of a helix reversal and less so on the concentration of aggregating material. Outside the long-chain limit, we find the reverse--that is, a strong concentration dependence and a weak dependence on the helix-reversal energy. Our treatment gives an excellent agreement with recently published circular-dichroism measurements on mixed aggregates of discotic molecules in the solvents water and n-butanol, at two different overall concentrations.     

Side‐chain supramolecular polymers with induced supramolecular chirality through H‐bonding interactions

Side‐chain supramolecular polymers that show columnar mesomorphism have been prepared through H‐bonding interactions between a polyvinylpyridine polymer as H‐acceptor and different H‐donors derived from benzoic acid. These compounds have been designed according to a promesogenic structure, that is, either disk‐like or banana‐like, to promote stacking and therefore the formation of columnar arrangements. IR studies confirmed the formation of H‐bonds and demonstrated that the H‐bond intensity decreases upon increasing temperature. The mesophase organizations were studied by polarized optical microscopy, differential scanning calorimetry, and X‐ray diffraction. Associations containing poly‐3‐methyl‐4‐vinylpyridine showed supramolecular optical activity, as evidenced by circular dichroism studies on thin films. It is proposed that these supramolecular polymers adopt a helical structure that can be biased toward a given handedness by virtue of the configuration of the stereogenic centers in the peripheral tails of the acids. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5528–5541, 2008