Enhanced Electric Polarization and Polar Switching of Dipolar Aromatic Liquids Confined in Supramolecular Gel Networks.

Dipolar aromatic liquids confined in the interstitial domains of chiral organogels show significantly enhanced electric polarization, as compared with those of pure liquids alone or organogels formed with nonpolar liquids. Intriguingly, nitrobenzene gels showed a supramolecular polar switching phenomenon; i.e., hysteresis in the polarization (P)-electric field (E) curves was observed for the gel above the melting point of the solvent. This indicates that the nitrobenzene molecules confined in the chiral nanofibrous gel networks exert macroscopic polarization whose direction is inversed depending on the direction of the external electric field. The anomalously enhanced electric polarization and polar switching phenomenon of supramolecular gels in varied solvents are scrutinized by the positive-up-negative-down (PUND) measurements, and the interactions between the gel nanofibers and the polar solvent molecules play crucial roles for the emergence of the polar switching phenomenon. This work presents for the first time that dipolar liquid molecules filling the interstitial space of supramolecular gels exhibit a significant confinement effect. It provides a new perspective to design electric-field-responsive soft materials based on the functional liquid domains confined in their porous networks.

Ferroelectric Coordination Polymers Self-Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands.

A new class of ferroelectric coordination-based polymers has been developed by the self-assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination-based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization-electric field (P-E) loops and inversion current peaks in current-voltage (I-V) loops. The observed ferroelectric properties are explainable by flip-flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive-up-negative-down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.

Self-assembly of a catechol-based macrocycle at the liquid-solid interface: experiments and molecular dynamics simulations.

This combined experimental (STM, XPS) and molecular dynamics simulation study highlights the complex and subtle interplay of solvent effects and surface interactions on the 2-D self-assembly pattern of a Schiff-base macrocycle containing catechol moieties at the liquid-solid interface. STM imaging reveals a hexagonal ordering of the macrocycles at the n-tetradecane/Au(111) interface, compatible with a desorption of the lateral chains of the macrocycle. Interestingly, all the triangular-shaped macrocycles are oriented in the same direction, avoiding a close-packed structure. XPS experiments indicate the presence of a strong macrocycle-surface interaction. Also, MD simulations reveal substantial solvent effects. In particular, we find that co-adsorption of solvent molecules with the macrocycles induces desorption of lateral chains, and the solvent molecules act as spacers stabilizing the open self-assembly pattern.

Prussian blue nanocontainers: selectively permeable hollow metal-organic capsules from block ionomer emulsion-induced assembly.

Hollow polymer-based particles are useful for the encapsulation, protection, and release of active compounds. Adding a metal-organic coordination framework shell to nanocontainers is an attractive goal because it should help control their stability and permeability while yielding new properties and functions. We have discovered that polymer capsules with a Prussian blue analogue inner shell can be synthesized by emulsion-induced assembly of a metal-containing amphiphilic block ionomer. The capsules are selectively permeable and were used as nanocontainers to encapsulate and release a model compound. Further, these nanomaterials are tunable in size and organize into 2-D close-packed arrays in the solid state. Potential applications for these materials include the encapsulation and nanopatterning of pharmaceutical, biological, and catalytic compounds.

Spontaneous hierarchical assembly of crown ether-like macrocycles into nanofibers and microfibers induced by alkali-metal and ammonium salts.

Schiff base macrocycle 1, which has a crown ether like central pore, was combined with different alkali-metal and ammonium salts in chloroform, resulting in one-dimensional supramolecular aggregates. The ion-induced self-assembly was studied with solid-state NMR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). It was found that the lengths and widths of the superstructures depend on the cation and counteranion of the salts. Among the salts being used, Na(+) and NH(4) (+) ions with BF(4) (-) ions showed the most impressive fibrous structures that can grow up to 1 mum in diameter and hundreds of microns in length. In addition, the size of the fibers can be controlled by the evaporation rate of the solvent. A new macrocycle with bulky triptycenyl substituents that prevent supramolecular assembly was prepared and did not display any nanofibers with alkali-metal ions in chloroform when studied with TEM.

Supramolecular assembly of carbohydrate-functionalized salphen-metal complexes.

Metallosalphen complexes with peripheral glucose and galactose substituents were synthesized and characterized. Their self-assembled supramolecular structures were then studied with transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). It was found that all of the complexes displayed aggregation in the solid-state. Zinc-salphen complexes showed a remarkably homogeneous helical nanofibrillar morphology, whereas the other metal complexes only displayed micron-sized clusters.

Electrochemical Thermoelectric Conversion with Polysulfide as Redox Species.

Thermocells convert waste heat to electricity without any pollution; however, the high cost and corrosivity of redox species hinder their commercialization. In this work, a thermocell that utilizes abundant polysulfide as redox species was demonstrated for the first time. 1-Butyl-1-methylpyrrolidinium polysulfide [(P14 )2 S3 ] was synthesized, and the redox species were prepared by the addition of sulfur to the (P14 )2 S3 solution in DMSO. In thermoelectric measurements, the Seebeck coefficient changed from -0.68 to +0.5 mV K-1 through addition of sulfur to the cell. Operando UV/Vis spectroscopy and open-circuit voltage analysis revealed that this effect was attributed to the change in the dominating redox reactions by the addition of sulfur. This result also provides a thermodynamic view on polysulfides electrochemistry, which is of high importance for lithium-sulfur batteries.

Reversible-irreversible approach to Schiff base macrocycles: access to isomeric macrocycles with multiple salphen pockets.

We have developed methodology for the formation of a new family of metal-free Schiff base macrocycles utilizing the differential exchange rates of aldimines and ketimines. The more robust ketimine bond is kinetically inert under the milder conditions used for aldimine bond formation. In particular, this route enables access to the first conjugated macrocycles with four unsymmetrical N2O2 salphen-like pockets.

Social and antisocial [3 + 3] Schiff base macrocycles with isomeric backbones.

Two new conjugated macrocycles have been prepared in high yield using Schiff base condensation. These are the first Schiff base macrocycles to incorporate phenanthrene, and they contain 66 and 78 atoms, respectively, in their smallest closed ring. Although the backbones of the two macrocycles have nearly the same constitution, one aggregates in chloroform while the other does not. This is rationalized based on the differential overlap of aromatic components in the dimers.

[6 + 6] Schiff-base macrocycles with 12 imines: giant analogues of cyclohexane.

Hexagon-shaped [6 + 6] Schiff-base macrocycles with 12 imine bonds are reported. These giant macrocycles possess 6 N2O2 coordination environments and mass spectrometry evidence for hexametallation of one macrocycle is provided. Semi-empirical calculations reveal two stable conformations with boat and chair geometries for the macrocycles metallated with Ni(II), analogous to the conformations observed for cyclohexane.

Fibrous aggregates from dinuclear zinc(II) salphen complexes.

Metal complexes composed of two zinc(II) salphen units that are bridged by a flexible hydrocarbon chain have been synthesized and characterized. Their self-assembled supramolecular structures were studied with transmission electron microscopy (TEM) and scanning electron microscopy (SEM). It was found that all of the complexes displayed nanofibrillar morphology and that the surface texture and diameter can be altered by the addition of 4,4'-bipyridine and hydrophobic effects, respectively.

Bimetallic Schiff base complexes: models for conjugated shape-persistent metallopolymers.

New Schiff base ligands with two metal binding sites have been prepared. Copper and zinc complexes of the ligands, which serve as models for rigid, conjugated metallopolymers, were synthesized and characterized. The copper complexes display only weak intramolecular antiferromagnetic interactions, suggesting that the polymer structure is not useful for developing magnetic materials. Preliminary investigations of the novel polymers, including the preparation of a conjugated zinc-containing polymer, are reported.

Synthesis, structure, and computational studies of soluble conjugated multidentate macrocycles.

[Chemical reaction: See text] Conjugated, shape-persistent macrocycles based on [3 + 3] Schiff-base condensation are of interest for supramolecular materials. In an effort to develop new discotic liquid crystals based on these compounds, a series of macrocycles with peripheral alkoxy groups of varying length have been prepared. The synthesis and mechanism of formation have been probed by isolation of oligomeric intermediates. A single-crystal X-ray diffraction study of one macrocycle revealed a nonplanar, strongly hydrogen-bonded structure. To our surprise, even with very long substituents, the macrocycles were not liquid crystalline. This has been rationalized by ab initio calculations that indicate the macrocycles are undergoing rotation of the dihydroxydiiminobenzene rings that may not allow a stable discotic liquid crystalline phase. These results provide new insight into the formation and properties of these large macrocycles and may provide guidance to developing stable liquid crystalline materials in the future.