Self-assembly of semifluorinated dendrons attached to electron-donor groups mediates their pi-stacking via a helical pyramidal column

Semifluorinated first-generation self-assembling dendrons attached via a flexible spacer to electron-donor molecules induce pi-stacking of the donors in the center of a supramolecular helical pyramidal column. These helical pyramidal columns self-organize in various columnar liquid crystal phases that mediate self-processing of large single crystal liquid crystal domains of columns and self-repair their intracolumnar structural defects. In addition, all supramolecular columns exhibit a columnar phase at lower temperatures that maintains the helical pyramidal columnar supramolecular structure and displays higher intracolumnar order than that in the liquid crystals phases. The results described here demonstrate the universality of this concept, the power of the fluorous phase or the fluorophobic effect in self-assembly and the unexpected generality of pyramidal liquid crystals.     

Thermotropic mesomorphism of soft materials bearing carboxylate-supported mu4-oxo tetracupric clusters

A new ligand containing long alkyl (octadecyl) chains was used to obtain the mesogenic complex [L2Cu4(mu4-O)(OAc)4].EtOH (1). This complex was thoroughly characterized and had its molecular structure solved by X-ray diffraction (XRD). Mesomorphic properties were demonstrated by means of polarized microscopy, differential scanning calorimetry, and XRD.     

A new approach to reduction of the Neumann problem in acoustic scattering to a non-hypersingular integral equation

The Neumann problem for the propagative Helmholtz equation inthe exterior of several bodies (obstacles) is studied in twoand three dimensions by a special modification of the boundaryintegral equation method. This modification can be called the'method of interior boundaries', because additional boundariesare introduced inside scattering bodies. The solution of theproblem is obtained in the form of a single layer potentialon the whole boundary. The density in the potential satisfiesthe uniquely solvable Fredholm equation of the second kind andcan be computed by standard codes. In fact our method holdsfor any positive wave numbers.     

Metal-insulator crossover in high T c cuprates: A gauge field approach

A metal-insulator crossover appears in the experimental data for in-plane resistivity of underdoped cuprates and a range of superconducting cuprates in the presence of a strong magnetic field suppressing superconductivity. We propose an explanation for this phenomenon based on a gauge field theory approach to the t-J model. In this approach, based on a formal spin-charge separation, the low energy effective action describes gapful spinons (with a theoretically derived doping dependence of the gap m _s ² ∼ δ| ln δ|) and holons with finite Fermi surface (ɛF ∼ tδ) interacting via a gauge field whose basic effect on the spinons is to bind them into overdamped spin waves, shifting their gap by a damping term linear in T, which causes the metal-insulator crossover. The presence of a magnetic field perpendicular to the plane acts by increasing the damping, in turn producing a big positive transverse in-plane magnetoresistance at low T, as experimentally observed.     

Thermotropic behaviour,self-assembly and photophysical properties of a series of squaraines

A series of squaraine dyes, based on 2,4-bis[4-(N,N-di-n-alkylamino)-2-hydroxyphenyl] squaraine including ethyl, propyl, butyl, pentyl, hexyl and heptyl derivatives, were synthesised by condensation of the corresponding 4-(N,N-di-n-alkylamino)-2-hydroxyphenol with squaric acid. The thermal behaviour of the series was recorded using both thermogravimetic analysis and differential scanning calorimetry while their crystalline structures were elucidated via single-crystal X-ray diffraction. The length of the alkyl chain proved to have a significant effect on both the thermotropic behaviour and the crystalline structure of the squaraine series. Two derivatives, butyl and heptyl, revealed the presence of liquid crystalline mesophases, smectic and nematic, respectively, which were confirmed and characterised via polarised light microscopy and X-ray diffraction. Several of the derivatives formed H- and/or J-aggregates upon thin film formation via spin coating before and after the thermal annealing treatment as indicated by UV–vis spectroscopy. The molecular and crystal structure, aggregation and thermal behaviour provide insight into the supramolecular assembly of this important class of materials. Photophysical measurements revealed large molar absorptivity, reasonably high fluorescence quantum yields and significant fluorescence anisotropy by making these derivatives suitable candidates for a number of electro-optic and photonics applications.     

Hollow spherical supramolecular dendrimers

The synthesis of a library containing 12 conical dendrons that self-assemble into hollow spherical supramolecular dendrimers is reported. The design principles for this library were accessed by development of a method that allows the identification of hollow spheres, followed by structural and retrostructural analysis of their Pm3n cubic lattice. The first hollow spherical supramolecular dendrimer was made by replacing the tapered dendron, from the previously reported tapered dendritic dipeptide that self-assembled into helical pores, with its constitutional isomeric conical dendron. This strategy generated a conical dendritic dipeptide that self-assembled into a hollow spherical supramolecular dendrimer that self-organizes in a Pm3n cubic lattice. Other examples of hollow spheres were assembled from conical dendrons without a dipeptide at their apex. These are conical dendrons originated from tapered dendrons containing additional benzyl ether groups at their apex. The inner part of the hollow sphere assembled from the dipeptide resembles the path of a spherical helix or loxodrome and, therefore, is chiral. The spheres assembled from other conical dendrons are nonhelical, even when they contain stereocenters on the alkyl groups from their periphery. Functionalization of the apex of the conical dendrons with diethylene glycol allowed the encapsulation of LiOTf and RbOTf in the center of the hollow sphere. These experiments showed that hollow spheres function as supramolecular dendritic capsules and therefore are expected to display functions complementary to those of other related molecular and supramolecular structures.