Cold Crystallization of Ferrocene-Hinged π-Conjugated Molecule Induced by the Limited Conformational Freedom of Ferrocene.

Crystallization that proceeds above the glass transition temperature upon heating the glassy or amorphous state is referred to as "cold crystallization", which has often been observed in supercooled phases of molecular materials followed by the transition to the thermodynamically stable crystalline phase. Although this behavior is common for the macromolecules with high structural flexibility among segments preserving the wide temperature range of corresponding glassy phases, cold crystallization of small molecules is relatively rare and there is still less knowledge on the design guideline of such molecules. Here we report a ferrocene-hinged molecule carrying two units of didodecyl-substituted pentathiophenes at the 1,1'-positions.

Photoinitiated Marangoni flow morphing in a liquid crystalline polymer film directed by super-inkjet printing patterns.

Slight contaminations existing in a material lead to substantial defects in applied paint. Herein, we propose a strategy to convert this nuisance to a technologically useful process by using an azobenzene-containing side chain liquid crystalline (SCLCP) polymer. This method allows for a developer-free phototriggered surface fabrication.

Proton-Rocking-Chair-Type Redox Capacitors Based on Indium Tin Oxide Electrodes with Multilayer Films Containing Ru Complexes.

A rechargeable proton-rocking-chair-type redox capacitor was fabricated using scalable layer-by-layer-(LbL)-assembled films composed of two dinuclear Ru complexes that exhibit proton-coupled electron-transfer (PCET) reactions with different Ru(II/III) redox potentials (RuNH-OH and RuCH-OH). RuNH-OH and RuCH-OH contain different coordination environments that involve two phosphonate linker ligands at both ends and bridging 2,6,2',6'-tetrakis(benzimidazol-2-yl)-4,4'-bipyridine or 1,3,1',3'-tetrakis(benzimidazol-2-yl)-5,5'-biphenyl ligands, respectively. The molecular units were assembled onto indium tin oxide (ITO) electrodes by complexation between the phosphonate groups and zirconium(IV) ions.

Acid-Group-Content-Dependent Proton Conductivity Mechanisms at the Interlayer of Poly(N-dodecylacrylamide-co-acrylic acid) Copolymer Multilayer Nanosheet Films.

The effect of the content of acid groups on the proton conductivity at the interlayer of polymer-nanosheet assemblies was investigated. For that purpose, amphiphilic poly(N-dodecylacrylamide-co-acrylic acid) copolymers [p(DDA/AA)] with varying contents of AA were synthesized by free radical polymerization. Surface pressure (π)-area (A) isotherms of these copolymers indicated that stable polymer monolayers are formed at the air/water interface for AA mole fraction (n) ≤ 0.

Photo-Responsive Soft Ionic Crystals: Ion-Pairing Assemblies of Azobenzene Carboxylates.

This report delineates the design and synthesis of negatively charged azobenzene derivatives that form photo-responsive ion-pairing assemblies. The azobenzene carboxylates possessing aliphatic chains were prepared as photo-responsive anions that promote the formation of ion-pairing dimension-controlled assemblies, including mesophases, when used in conjunction with a tetrabutylammonium (TBA) cation. The photo-responsive properties of the ion pairs and the precursory carboxylic acids in the bulk state were examined by polarized optical microscopy (POM) and X-ray diffraction (XRD), demonstrating that liquid crystal (LC)-liquid and crystal-liquid phase transitions occurred, depending on the number and lengths of the aliphatic chains of each assembly.

Photoalignment of Vertically Oriented Microphase Separated Lamellae in LC-LC Diblock Copolymer Thin Film.

The microphase separation and photoalignment behavior of a diblock copolymer consisting of two kinds of side chain liquid crystalline (LC) polymers are investigated. Here, the mesogens of photoresponsive azobenzene and non-photoresponsive cyanobiphenyl are introduced in the side chains. The azobenzene and cyanobiphenyl mesogens orient homeotropically and planarly, respectively, in a thin film state.

High-Density Liquid-Crystalline Polymer Brushes Formed by Surface Segregation and Self-Assembly.

High-density polymer brushes on substrates exhibit unique properties and functions stemming from the extended conformations due to the surface constraint. To date, such chain organizations have been mostly attained by synthetic strategies of surface-initiated living polymerization. We show herein a new method to prepare a high-density polymer brush architecture using surface segregation and self-assembly of diblock copolymers containing a side-chain liquid-crystalline polymer (SCLCP).

Proton Conductivities of Lamellae-Forming Bioinspired Block Copolymer Thin Films Containing Silver Nanoparticles.

Size-controlled metal nanoparticles (NPs) were spontaneously formed when the amphiphilic diblock copolymers consisting of poly(vinyl catechol) and polystyrene (PVCa-b-PSt) were used as reductants and templates for NPs. In the present study, the proton conductivity of well-aligned lamellae structured PVCa-b-PSt films with Ag NPs was evaluated. We found that the proton conductivity of PVCa-b-PSt film was increased 10-fold by the addition of Ag NPs into the proton conduction channels filled with catechol moieties.

Fabrication and Characterization of Cross-Linked Organic Thin Films with Nonlinear Mass Densities.

The preparation of urea (bonded) cross-linked multilayer thin films by sequential deposition of bifunctional and tetrafunctional molecular building blocks is demonstrated. Multilayer growth as a function of deposition cycles was inspected using UV-vis absorption spectroscopy. From infrared results, three characteristic infrared bands of amide I, amide II, and asymmetric νa(N-C-N) stretching confirmed the formation of polyurea networks by alternate dipping into solutions of amine and isocyanate functionality monomers.

Inducing Planar Orientation in Side-Chain Liquid-Crystalline Polymer Systems via Interfacial Control.

For efficient photoresponses of liquid-crystal (LC) azobenzene (Az) polymer systems, planar LC orientation of the Az mesogenic group is required because the light irradiation process usually occurs with normal incidence to the film surface. However, LC molecules with a rodlike shape tend to orient perpendicularly to the film surface according to the excluded volume effect theory. This review introduces new approaches for inducing planar orientation in side-chain LC Az polymer films via interface and surface molecular designs.

Free Surface Command Layer for Photoswitchable Out-of-Plane Alignment Control in Liquid Crystalline Polymer Films.

To date, reversible alignment controls of liquid crystalline materials have widely been achieved by photoreactive layers on solid substrates. In contrast, this work demonstrates the reversible out-of-plane photocontrols of liquid crystalline polymer films by using a photoresponsive skin layer existing at the free surface. A polymethacrylate containing a cyanobiphenyl side-chain mesogen adopts the planar orientation.

Coulomb Blockade in a Two-Dimensional Conductive Polymer Monolayer.

Electronic transport was investigated in poly(3-hexylthiophene-2,5-diyl) monolayers. At low temperatures, nonlinear behavior was observed in the current-voltage characteristics, and a nonzero threshold voltage appeared that increased with decreasing temperature. The current-voltage characteristics could be best fitted using a power law.

Alternation of Side-Chain Mesogen Orientation Caused by the Backbone Structure in Liquid-Crystalline Polymer Thin Films.

In side-chain-type liquid-crystalline (LC) polymers, the main chain rigidity significantly affects the LC structure and properties. We show herein a relevant new effect regarding the orientation of side-chain mesogenic groups of LC polymers in a thin-film state. A subtle change in the main chain structure, i.

High proton conductivity in the molecular interlayer of a polymer nanosheet multilayer film.

High proton conductivity was achieved in a polymer multilayer film with a well-defined two-dimensional lamella structure. The multilayer film was prepared by deposition of poly(N-dodecylacryamide-co-acrylic acid) (p(DDA/AA)) monolayers onto a solid substrate using the Langmuir-Blodgett technique. Grazing-angle incidence X-ray diffraction measurement of a 30-layer film of p(DDA/AA) showed strong diffraction peaks in the out-of-plane direction at 2θ = 2.

Free-surface molecular command systems for photoalignment of liquid crystalline materials.

The orientation of liquid crystal molecules is very sensitive towards contacting surfaces, and this phenomenon is critical during the fabrication of liquid crystal display panels, as well as optical and memory devices. To date, research has focused on designing and modifying solid surfaces. Here we report an approach to control the orientation of liquid crystals from the free (air) surface side: a skin layer at the free surface was prepared using a non-photoresponsive liquid crystalline polymer film by surface segregation or inkjet printing an azobenzene-containing liquid crystalline block copolymer.

Photoinduced Volume Transition in Liquid Crystalline Polymer Gels Swollen by a Nematic Solvent.

Nematic liquid crystalline (LC) cross-linked polymer gel sheets containing 3 mol % azobenzene (Az) unit were prepared and swollen by a nematic solvent of 4'-pentyl-4-cyanobiphenyl (5CB). This 5CB-swollen gel sheet exhibited a discontinuous volume change around the nematic-isotoropic phase transition temperature of the LC gel (). UV irradiation at a temperature slightly lower than provoked a large volume transition (expansion) due to a loss of nematic order within the gel sheet caused by the trans-to-cis photoisomerization of Az.

Rearrangement of the cyclohexadiene derivatives of C60 to bis(fulleroid) and bis(methano)fullerene: structure, stability, and mechanism.

The cyclohexadiene derivative of C(60) rearranges photochemically to bis(fulleroid) (two [6,5] open structure) and bis(methano)fullerene (two [6,6] closed structure). During this process, a [6,5] open/[6,6] closed intermediate is observed. The isolated intermediate undergoes photochemical rearrangement to bis(fulleroid) and bis(methano)fullerene.