Supercooling of functional alkyl-π molecular liquids.

Metastable states of soft matters are extensively used in designing stimuli-responsive materials. However, the non-steady properties may obstruct consistent performance. Here we report an approach to eradicate the indistinguishable metastable supercooled state of functional molecular liquids (FMLs), which remains as a liquid for weeks or months before crystallizing, rational molecular design.

Topological Control of Columnar Stacking Made of Liquid-Crystalline Thiophene-Fused Metallonaphthalocyanines.

The spontaneous organization of two-dimensional polyaromatic molecules into well-defined nanostructures through noncovalent interactions is important in the development of organic-based electronic and optoelectronic devices. Two regioisomers of thiophene-fused zinc naphthalocyanines ZnTNcendo and ZnTNcexo have been designed and synthesized to obtain photo- and electroactive liquid crystalline materials. Both compounds exhibited liquid crystalline behavior over a wide temperature range through intermolecular π-π interactions and local phase segregation between the aromatic cores and peripheral side chains.

Molecular Designs for Enhancement of Polarity in Ferroelectric Soft Materials.

The racemic oxovanadium(IV) salmmen complexes, [VO((rac)-(4-X-salmmen))] (X = C12C10C5 (1), C16 (2), and C18 (3); salmmen = N,N'-monomethylenebis-salicylideneimine) with "banana shaped" molecular structures were synthesized, and their ferroelectric properties were investigated. These complexes exhibit well-defined hysteresis loops in their viscous phases, moreover, 1 also displays liquid crystal behaviour. We observed a synergetic effect influenced by three structural aspects; the methyl substituents on the ethylene backbone, the banana shaped structure and the square pyramidal metal cores all play an important role in generating the observed ferroelectricity, pointing the way to a useful strategy for the creation of advanced ferroelectric soft materials.

Preparation of a cyclic polyphenylene array for a zigzag-type carbon nanotube segment.

Preparation of cyclic polyphenylene array 2, which corresponds to a complete carbon array of a zigzag-type CNT segment with (18,0)-structure, has been established by a Diels-Alder reaction of cyclic biphenylylene-acetylene derivative 1 with tetraphenylcyclopentadienone. The reaction of 2 with excess FeCl3 realized a presumed cyclodehydrogenation reaction and elimination of the alkyl chains that were introduced as a measure to counter the low solubility problem, but this resulted in the formation of a complicated mixture that included the mass region of a presumed zigzag-type CNT segment with (18,0)-structure. The rather efficient blue emission of cyclic compounds 1 and 2 was discussed utilizing fluorescence (FL) quantum efficiencies (Φ(FL)) and lifetimes (τ(FL)) in their crystalline state along with those in dichloromethane solution.

Ion-pair-based assemblies comprising pyrrole-pyrazole hybrids.

Modified 3,5-dipyrrolylpyrazole (DPP) derivatives in their protonated form produce planar [2+2]-type complexes with trifluoroacetate (TFA) ions. These complexes serve as constituent components of ion-pair-based assemblies. An essential strategy for the construction of dimension-controlled organized structures based on these [2+2]-type complexes is the introduction of aryl rings bearing long alkyl chains, which enables the formation of 2D patterns at interfaces, supramolecular gels, and mesophases.

Discotic columnar mesophases derived from 'rod-like'pi-conjugated anion-responsive acyclic oligopyrroles.

Rod-like pi-conjugated anion-responsive acyclic oligopyrroles have been reported to form stacked disk-like components that result in the formation of discotic columnar mesophases as thermotropic liquid crystals.

Spin transition at the mesophase transition temperature in a cobalt(II) compound with branched alkyl chains.

A cobalt(II) compound, [Co(C5C12C10-terpy)2](BF4)2 [C5C12C10-terpy = 4',5' ''-decyl-1' ''-(heptadecyloxy)-2,2':6',2' '-terpyridine] with branched alkyl chains, based on a terpyridine frame, was synthesized. The cobalt(II) compound exhibits a spin transition between low-spin and high-spin with a thermal hysteresis loop (T(1/2) upward arrow = 288 K and T(1/2) downward arrow = 284 K) at the liquid-crystal transition temperature. It is the first example in the cobalt(II) compounds in which the spin transition occurs at the crystal-liquid crystal transition temperature.

Self-organization of low-symmetry adjacent-type metallophthalocyanines having branched alkyl chains.

Low-symmetry, adjacent-type metallophthalocyanines 1 and 2 with four branched alkyl chains on one side and a chiral bridging segment on the other were synthesized, and their self-organization properties were investigated. The synthesized adjacent-type phthalocyanines were liquid-crystalline and exhibited a phase transition from the crystalline phase to the mesophase below room temperature. X-ray diffraction indicated that the molecules are stacked in one-dimensional columnar aggregates with a hexagonal arrangement.

Synthesis and properties of hexakis(6-octyl-2-azulenyl)benzene as a multielectron redox system with liquid crystalline behavior.

[structure: see text] This paper describes the cyclotrimerization reaction of di(2-azulenyl)acetylenes (2a,b) catalyzed by Co2(CO)8 to produce hexa(2-azulenyl)benzene derivatives (1a,b). The cyclooligomerization of 2a and 2b utilizing CpCo(CO)2 as a catalyst produced (eta5-cyclopentadienyl)[tetra(2-azulenyl)cyclobutadiene]cobalt complexes (3a,b). The redox behavior of hexakis(6-octyl-2-azulenyl)benzene (1b), bis(6-octyl-2-azulenyl)acetylene (2b), and the cobalt complexes 3a and 3b along with 6-octyl-2-phenylazulene (19) was examined by cyclic voltammetry (CV).

Nanoscopic fibrous assemblies made of metallophthalocyanine-terminated amphiphilic polymers.

Atom-transfer radical polymerization (ATRP) of acrylates from the initiator-modified zinc phthalocyanine yielded amphiphilic, phthalocyanine-terminated polymers with a narrow molecular-weight distribution. The disklike phthalocyanine moiety was incorporated into one end of the polymer chain. We investigated the aggregation behavior of phthalocyanine-terminated polymers in solution and in the solid state by using UV-visible, FT-IR, differential scanning calorimetry (DSC), and temperature-controlled powder X-ray diffraction (XRD) measurements.

Preparation of organic-inorganic composites containing rod-like phthalocyanine polymers.

Sol-gel polymerization of tetraethoxysilane in the presence of amphiphilic phthalocyanine polymer 2 produced organic-inorganic composites with the rod-like phthalocaynine polymers incorporated within ordered hexagonal channels.

Self-assembly and regioselective photodimerization of anthracene having a dendritic substituent.

[reaction: see text] Thermotropic liquid crystallinity can be induced for an anthracene having a dendritic substituent. The photodimerization reaction of an anthracene moiety in the smectic phase proceeded quantitatively and regioselectively.

Selective ligation to sterically isolated metallophthalocyanines.

A new class of sterically hindered phthalocyanine has been synthesized and characterized. Pentaphenylbenzene units were introduced at the periphery of each phthalocyanine to yield a sterically protected metal center. The attachment of the bulky oligophenylbenzene units resulted in the complete isolation of individual MPc molecules.

Synthesis of poly(6-azulenylethynyl)benzene derivatives as a multielectron redox system with liquid crystalline behavior.

A series of poly(6-azulenylethynyl)benzenes substituted with n-hexyloxycarbonyl chains at 1,3-positions in azulene rings, i.e., hexakis-, 1,2,4,5-tetrakis-, 1,3,5-tris-, and 1,4-bis(6-azulenylethynyl)benzene derivatives 1, 2, 3, and 4b, have been prepared by a simple one-pot reaction involving repeated Pd-catalyzed alkynylation of halogenated arenes with substituted 6-ethynylazulene and/or ethynylated arenes with substituted 6-bromoazulene under Sonogashira-Hagihara conditions.

Self-organization of supramolecular complex composed of rigid dendritic porphyrin and fullerene.

A second-generation 1,3,5-phenylene-based dendritic porphyrin decorated with flexible alkyl chains exhibited a liquid crystallinity, and the inclusion of fullerene within the nanospace of the dendritic porphyrin strongly affected the mesophase structure in the thermotropic liquid-crystalline phase.