Covalently Trapped Triarylamine-Based Supramolecular Polymers

C₃-Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π–π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology. The results presented here clearly evidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalent capture whereas the mechanical properties of the gels are concomitantly improved, with an increase of their storage modulus by two orders of magnitude.     

Micro-wires self-assembled and 3D-connected with the help of a nematic liquid crystal

We discuss a method for producing automatic 3D connections at right places between substrates in front of one another. The idea is based on the materialization of disclination lines working as templates. The lines are first created in the nematic liquid crystal (5CB) at the very place where microwires have to be synthesized. Due to their anchoring properties, colloids dispersed into the nematic phase produce orientational distortions around them. These distortions, which may be considered as due to topological charges, result in a nematic force, able to attract the colloids towards the disclinations. Ultimately, the particles get trapped onto them, forming micro- or nano-necklaces. Before being introduced in the nematic phase, the colloids are covered with an adhering and conducting polypyrrole film directly synthesized at the surface of the particles (heterogeneous polymerization). In this manner, the particles become conductive so that we may finally perform an electropolymerization of pyrrole monomers solved in 5CB, and definitely stick the whole necklace. The electric connection thus synthesized is analyzed by AFM, and its strength is checked by means of hydrodynamic tests. This wiring method could allow Moore's law to overcome the limitations that arise when down-sizing the electronic circuits to nanometer scale.     

Use of high-temperature differential scanning calorimetry to investigate the β–α transition in calcium pyrophosphate

High-temperature differential scanning calorimetry was used to investigate the thermodynamic parameters of the γ–β and β–α transitions in calcium pyrophosphate (Ca₂P₂O₇). The measured enthalpy of transition compared well with previous results when higher heating rates (≥20 K min^?1) were used. Recommendations for optimal use of HTDSC in high-temperature phase transition measurements are presented.     

Study of the reciprocal space image of the biaxial nematic phase in the plane of the amphiphilic bilayer

High resolution synchrotron X-ray measurements have been performed on the uniaxial and biaxial phases of the lyotropic mixture potassuim laurate, decanol and water. An elegant magnetic orientational procedure allows us to obtain the cut of the reciprocal space image of the biaxial phase at the plane perpendicular to the amphiphilic bilayer. The analysis of densitometric profiles of the diffracted bands indicate an anisotropic micellar correlation in the plane of the amphiphilic bilayer. It is suggested that an anisotropic distribution of decanol and potassium laurate in this plane could be responsible for this effect.     

Experimental characterization of the weakly anisotropic CN X 2Σ+ + Ne potential from IR-UV double resonance studies of the CN-Ne complex

IR-UV double resonance spectroscopy has been used to characterize hindered internal rotor states (n(K) = 0(0), 1(1), and 1(0)) of the CN-Ne complex in its ground electronic state with various degrees of CN stretch (ν(CN)) excitation. Rotationally resolved infrared overtone spectra of the CN-Ne complex exhibit perturbations arising from Coriolis coupling between the closely spaced hindered rotor states (1(1) and 1(0)) with two quanta of CN stretch (ν(CN) = 2). A deperturbation analysis is used to obtain accurate rotational constants and associated average CN center-of-mass to Ne separation distances as well as the coupling strength. The energetic ordering and spacings of the hindered internal rotor states provide a direct reflection of the weakly anisotropic intermolecular potential between CN X (2)Σ(+) and Ne, with only an 8 cm(-1) barrier to CN internal rotation, from which radially averaged anisotropy parameters (V(10) and V(20)) are extracted that are consistent for ν(CN) = 0-3. Complementary ab initio calculation of the CN X (2)Σ(+) + Ne potential using MRCI+Q extrapolated to the complete one-electron basis set limit is compared with the experimentally derived anisotropy by optimizing the radial potential at each angle. Experiment and theory are in excellent accord, both indicating a bent minimum energy configuration and nearly free rotor behavior. Analogous experimental and theoretical studies of the CN-Ne complex upon electronic excitation to the CN B (2)Σ(+) state indicate a slightly more anisotropic potential with a linear CN-Ne minimum energy configuration. The results from these IR-UV double resonance studies are compared with prior electronic spectroscopy and theoretical studies of the CN-Ne system.     

Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α‐Arylation of Alcohols through Photoredox,HAT, and Nickel Catalysis

The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol α‐hydroxy C?H bonds. This approach employs zinc‐mediated alcohol deprotonation to activate α‐hydroxy C?H bonds while simultaneously suppressing C?O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn‐based Lewis acids also deactivates other hydridic bonds such as α‐amino and α‐oxy C?H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3‐step synthesis of the drug Prozac exemplifies the utility of this new method.     

Biaxialite critique d'un smectique C

Measurements of the biaxiality of a smectic C as a function of the order parameter are presented for n-heptyloxybenzylidene-n-heptylanisol at the second order transition smectic A to smectic C. The experimental set up is a variation of the classical conoscopy method of interference.     

The commensurate and incommensurate TGBC^* liquid crystal phases

We propose complements to the Renn model of the liquid crystal TGBC^* phase. We argue that the rotation angle per helislab is spontaneously in the radian range, not too small to limit the energy cost of the twist grain boundaries between the helislabs, not too large to preserve the double twisting efficiency. Taking the elastic interactions between the helislabs into account, we show that the structure may undergo two different lock-ins, provided that the uncontrolled interactions at the sample surfaces are small enough. First, for appropriate values of the elastic constants, an angular lock-in may fix the rotation angle per helislab at values exactly commensurate to π. Three characteristic lengths of the TGBC^* phase, the TGB period and the thicknesses of both the smectic blocks and of the helislabs are then commensurate to one another, with moreover, integer ratios at the most efficient commensurabilities. The TGBC^* phase could thus exist in several versions, incommensurate and commensurate, according to the steps of a restricted Devil's staircase. A second elastic lock-in should then arise in the commensurate TGBC^* phases, to set the arrays of disclination lines between the helislabs in simple rectangular lattices, arranged in a helical manner. Being placed right behind one another, the disclination lines then coincide when observed along the TGB axis. This could explain the typical textures with square or hexagonal grids, observed in oriented samples. The commensurability of the TGBC^* phases could be analyzed with X-ray scattering experiments in the same manner as already reported for the TGBC phase. Received 30 November 1999 and Received in final form 5 May 2000