Predictable Synthesis of 3D Polymer Networks Using Crystal Component-Linking.

Controlled synthesis of 3D polymer networks presents a significant challenge because of the complexity of the polymerization reaction in solution. In this study, a polymerization system that facilitates the prediction of a polymer network structure via percolation simulations is realized. The most significant difference between general percolation simulations and experimental polymerization systems is the mobility of the molecules during the reaction.

Enhanced Orientation of Liquid Crystals Inside Micropores of Metal-Organic Frameworks Having Thermoresponsivity.

With the aim of controlling the orientation of liquid crystals (LCs) toward realizing external stimuli-responsive materials with tunable functionalities, we synthesized a composite of LCs and metal-organic frameworks (MOFs) by filling LCs into the pores of MOFs (LC@MOFs) for the first time. The included LCs interact with the MOFs through coordination bonds between the cyano groups of the LCs and the metal ions of the MOFs, enabling the orientation of the LC molecules inside the pores of the MOFs and the realization of birefringence of LC@MOFs. The three-dimensional nanometer interstice frameworks maintained the LC orientation even at temperatures much higher than the isotropic phase transition temperature of bulk LCs.

1,2-Disubstituted 1,2-Dihydro-1,2,4,5-tetrazine-3,6-dione as a Dynamic Covalent Bonding Unit at Room Temperature.

Dynamic covalent bonds are useful tools in a wide range of applications. Although various reversible chemical reactions have been studied for this purpose, the requirement for harsh conditions, such as high temperature and low or high pH, to activate generally stable covalent bonds limits their potential applications involving biomolecules or household utilization. Here, we report the design, synthesis, characterization, and dynamic covalent bonding properties of 1,2-disubstituted 1,2-dihydro-1,2,4,5-tetrazine-3,6-dione (TETRAD).

One-dimensional DABCO hydrogen-bonding chain in a hexagonal channel of magnetic [Ni(dmit)].

Crystals of (HDABCO+)9(DABCO)[Ni(dmit)2]9·6CH3CN were shown to have a space group of R3[combining macron], a hexapetal flower-like channel of [Ni(dmit)2] anions, and a one-dimensional hydrogen bonding chain composed of protonated DABCO and CH3CN molecules. The crystals display antiferromagnetic and ferromagnetic interactions within and between hexamers, respectively, whereas the flexible DABCO-CH3CN array shows dielectric relaxation.

Photoinduced Pyramidal Inversion Behavior of Phosphanes Involved with Aggregation-Induced Emission Behavior.

Invited for the cover of this issue is Kenta Kokado and co-workers at Hokkaido University. The cover picture describes the interesting pyramidal inversion behavior of phosphanes in the excited state, like entering "the Mirror World", which we found in this research. Read the full text of the article at 10.

Photoinduced Pyramidal Inversion Behavior of Phosphanes Involved with Aggregation-Induced Emission Behavior.

Aggregation-induced emission (AIE) is a fascinating phenomenon because of the applications of luminescent materials in the aggregated state, which exploit the large structural changes of the molecules in the excited state. Recently, it was reported that triphenylphosphane derivatives show AIE behavior in which they undergo potentially large structural changes in the excited state. Inspired by this report, photoinduced pyramidal inversion behavior of phosphanes was investigated.

Step-Growth Copolymerization Between an Immobilized Monomer and a Mobile Monomer in Metal-Organic Frameworks.

The A-A/B-B step-growth copolymerization between a monomer immobilized in the crystalline state and a monomer mobile in the solution state is demonstrated. One of the two monomers was immobilized as organic ligands of the metal-organic framework (MOF) and polymerized with the mobile guest monomer, resulting in the formation of linear polymers. The polymerization behavior was completely different from that of the solution polymerizations.

Consideration of Molecular Structure in the Excited State to Design New Luminogens with Aggregation-Induced Emission.

Aggregation-induced emission (AIE) is a photoluminescence phenomenon in which an AIE luminogen (AIEgen) exhibits intense emission in the aggregated or solid state but only weak or no emission in the solution state. Understanding the mechanism of AIE requires consideration of excited state molecular geometry (for example, a π twist). This Minireview examines the history of AIEgens with a focus on the representative AIEgen, tetraphenylethylene (TPE).

Crystal Crosslinked Gels for the Deposition of Inorganic Salts with Polyhedral Shapes.

Biomineralization has been given a great deal of attention by materials chemists because of its low environmental load and sustainability. With the goal of synthesizing such processes, various methods have been developed, especially for inorganic salts of calcium. In this report, we focused on the deposition of inorganic salts, such as calcium carbonate and calcium phosphate using crystal crosslinked gels (CCG), which are prepared by crystal crosslinking of metal-organic frameworks (MOFs).

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non-Polar Solvents by using Conductometry.

In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride () ion-pair salt to the free ions through complexation with -octamethylcalix[4]pyrrole (), which is a well-known receptor for chloride anions. In the presence of , the conductivity of increases in various non-polar solvents, indicating that complexation with enhances the ionic dissociation of in such non-polar solvents. In other words, recognizes chloride as an ion-paired salt as well as a free anion in non-polar solvents.

Box-like gel capsules from heterostructures based on a core-shell MOF as a template of crystal crosslinking.

New polymer capsules (PCs) were obtained using a crystal crosslinking (CC) method on core-shell MOF crystals. The latter are based on the epitaxial growth of two isostructural coordination polymers which are then selectively crosslinked. Decomposition of the non-reticulated phase leads to new PCs, possessing a well-defined hollow cubic shape reflecting the heterostructure of the template.

Lipophilic polyelectrolyte gel derived from phosphonium borate can absorb a wide range of organic solvents.

Herein, we demonstrate a polyelectrolyte gel which can absorb a wide range of organic solvents from dimethylsulfoxide (DMSO, permittivity: ε = 47.0) to tetrahydrofuran (ε = 5.6).

Motility of Microtubules on the Inner Surface of Water-in-Oil Emulsion Droplets.

Water-in-oil emulsion systems have recently attracted much attention in various fields. However, functionalization of water-in-oil emulsion systems, which is required for expanding their applications in industries and research, has been challenging. We now demonstrate the functionalization of a water-in-oil emulsion system by anchoring a target protein molecule.

Organic Reaction as a Stimulus for Polymer Phase Separation.

Molecular design of stimuli-sensitive polymers has been attracting considerable interest of chemists because of their latent ability to achieve smart materials. Heat, light, pH, and chemicals have been often utilized as a stimuli-inducing polymer phase transition from solution to aggregation and vice versa. In this report, as a new trigger for lower critical solution temperature (LCST)-type polymer phase transition, we introduce organic reaction of small organic molecules, not to the polymer chain itself.

Disassembly Control of Saccharide-Based Amphiphiles Driven by Electrostatic Repulsion.

According to the design of disassembly using electrostatic repulsion, novel amphiphiles consisting of a lipophilic ion part and a hydrophilic saccharide part were synthesized via the facile copper-catalyzed click reaction, and their molecular assemblies in water and chloroform were studied. The amphiphiles exhibited a molecular orientation opposite to that of the conventional amphiphiles in each case. ζ Potential measurements indicated that the lipophilic ion part is exposed outside in chloroform.

Liquefaction-induced emission enhancement of tetraphenylethene derivatives.

A typical AIE dye, TPE, was liquefied by attaching long and branched alkyl chains. The obtained liquid dye showed intense emission compared to the solid dye or TPE. The linkage between TPE and the alkyl chain led to significant difference in their photoluminescent and thermal properties.

Anisotropically Swelling Gels Attained through Axis-Dependent Crosslinking of MOF Crystals.

Anisotropically deforming objects have attracted considerable interest for use in molecular machines and artificial muscles. Herein, we focus on a new approach based on the crystal crosslinking of organic ligands in a pillared-layer metal-organic framework (PLMOF). The approach involves the transformation from crosslinked PLMOF to polymer gels through hydrolysis of the coordination bonds between the organic ligands and metal ions, giving a network polymer that exhibits anisotropic swelling.

Crystal Crosslinked Gels with Aggregation-Induced Emissive Crosslinker Exhibiting Swelling Degree-Dependent Photoluminescence.

The synthesis and photoluminescence properties of crystal crosslinked gels (CCGs) with an aggregation-induced emission (AIE) active crosslinker derived from tetraphenylethene (TPE) is discussed in this article. The CCG was prepared from a metal organic framework (MOF) with large pore aperture to allow the penetration of TPE crosslinker. The obtained CCG possessed a rectangular shape originated from the parent MOF, KUMOF.

Mesogenic Polyelectrolyte Gels Absorb Organic Solvents and Liquid Crystalline Molecules.

In this paper, mesogenic polyelectrolyte gels (MPEgels) tethering mesogenic groups on the side chains were synthesized from a mesogenic monomer and ionic monomer via a conventional radical polymerization process. The obtained MPEgels absorbed various organic solvents in a wide range of dielectric constants from chloroform (ε = 7.6) to DMSO (ε = 46.

Metal-organic framework tethering PNIPAM for ON-OFF controlled release in solution.

A smart metal-organic framework (MOF) exhibiting controlled release was achieved by modification with a thermoresponsive polymer (PNIPAM) via a surface-selective post-synthetic modification technique. Simple temperature variation readily switches "open" (lower temperature) and "closed" (higher temperature) states of the polymer-modified MOF through conformational change of PNIPAM grafted onto the MOF, resulting in controlled release of the included guest molecules such as resorufin, caffeine, and procainamide.

Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside.

Nano- and microsized cubic gel particles from cyclodextrin metal-organic frameworks.

Sweet cube o' mine: Bottom-up control of gel particles has been regarded as a great challenge. By employing internal cross-linking of cyclodextrin metal-organic frameworks, cubic sugar gels were formed with sharp edges that reflect the shape of the crystals. This enabled the fabrication of shape- and size-controlled polymer gels from porous crystals (see picture).

Fundamental molecular design for precise control of thermoresponsiveness of organic polymers by using ternary systems.

The de novo design of thermosensitive polymers in solution has been achieved by using the addition of small organic molecules (or "effectors"). Hydrogen bonding as an attractive polymer-polymer or polymer-effector interaction substantially dominates the responsivity, causing facile switching between LCST-type and UCST-type phase transitions, control of the transition temperature, and further coincidence of the two transitions. Small molecules having a high affinity for the polymer induce UCST-type phase behavior, whereas those having a low affinity for the polymer showed LCST-type phase behavior.

Aromatic Ring-Fused Carborane-Based Luminescent π-Conjugated Polymers.

A series of π-conjugated polymers linked by benzocarborane (1,2-(buta-1',3'-diene-1',4'-diyl)-1,2-dicarbadodecaborane) were synthesized via Sonogashira-Hagihara polycondensation reaction. The opened molecular structure of diiodo monomer containing benzocarborane resulted in fast polymerization and high molecular weights. The obtained polymers were fully characterized by (1) H, (13) C, and (11) B NMR spectroscopies.