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. A crystal component-linking method that connects the precisely arranged monomer as a supramolecular crystalline state to imitate the simple percolation theory is adopted. The percolation simulation based on the crystal structure of the arranged monomers is used to accurately calculate the gelation point, gel fraction, degree of swelling, and atomic formula, which correspond with the experimental results. This suggests that the network structures polymerized via the crystal component-linking method can be predicted precisely by a simple percolation simulation. Further, the percolation simulation predicts the structures of the loop, branched polymer, and crosslinking point, which are difficult to measure experimentally. The polymerization of precisely-arranged immobilized monomers in supramolecular structures is promising in synthesizing precisely controlled polymer networks.

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. Furthermore, the orientational state changed upon heating or cooling, inducing temperature-dependent birefringence. This study provides a new approach to the development of stimuli-responsive optical materials and stimuli-responsive MOFs.

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). Hetero-Diels-Alder reactions of TETRAD with furan derivatives and their retro-reactions proceeded rapidly at room temperature under neutral conditions, enabling a chemically induced sol-gel transition system.

One-dimensional DABCO hydrogen-bonding chain in a hexagonal channel of magnetic [Ni(dmit)2].

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 10.1002/chem.202000264.

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. In photochemical experiments, the prepared P-stereogenic phosphanes exhibited photoracemization in dilute solution, and a negative correlation was observed between the photoracemization and the AIE phenomenon. Theoretical computations revealed that the inversion barrier in the excited state was much smaller than that in the ground state. This is the first report on the photoinduced pyramidal inversion behavior of phosphanes, which will provide new and unexplored applications.

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. In particular, the degrees of polymerization (DP) converged to a specific value depending on the MOF structures. The inevitable termination is caused not by imperfectness of the polymerization reaction, but by the selection of the two polymerization partners among the several adjacent immobilized monomers. This is fully supported by the Monte Carlo simulation on the basis of the polymerization mechanism. Precise immobilization of monomers in the supramolecular assemblies is a promising way for the controlled A-A/B-B step-growth polymerization.

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). The mechanisms of solution-state quenching are reviewed and the crucial role of excited-state molecular transformations for AIE is discussed. Finally, recent progress in understanding the relationship between excited state molecular transformations and AIE is overviewed for a range of different AIEgens.

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 (TBACl) ion-pair salt to the free ions through complexation with meso-octamethylcalix[4]pyrrole (CP), which is a well-known receptor for chloride anions. In the presence of CP, the conductivity of TBACl increases in various non-polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non-polar solvents. In other words, CP recognizes chloride as an ion-paired salt as well as a free anion in non-polar solvents. Additionally, the TBA(CP-Cl) complex exhibited a considerably lower ion-pairing constant (Kip) than TBACl in non-polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli-responsive soft materials in organic solvents using coulombic forces.

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). The gel consists of polystyrene chains with small amounts (∼5 mol%) of lipophilic electrolytes derived from triphenylphosphonium tetraaryl borate. The swelling ability of the polyelectrolyte gel was higher than that of the alkyl ammonium tetraaryl borate previously reported by us, and this is attributed to the higher compatibility with organic solvents, as well as the higher dissociating ability, of the triphenyl phosphonium salt. The role of the ionic moieties was additionally confirmed by post modification of the polyelectrolyte gel via a conventional Wittig reaction, resulting in a nonionic gel. Our findings introduced here will lead to a clear-cut molecular design for polyelectrolyte gels which absorb all solvents.

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). Due to the crystalline nature of MOFs, CCGs intrinsically possess polyhedral shapes derived from the original MOF crystals. As the result of deposition, the obtained inorganic salts also exhibited a polyhedral shape derived from the CCG. The deposition mainly occurred near the surface of the CCG, and the amorphous nature of the deposited inorganic salts was also confirmed.

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. A microtubule (MT)-associated motor protein kinesin-1 was successfully anchored to the inner surface of water-in-oil emulsion droplets by employing the specific interaction of nickel-nitrilotriacetic acid-histidine tag. The MTs exhibited a gliding motion on the kinesin-functionalized inner surface of the emulsion droplets, which confirmed the success of the functionalization of the water-in-oil emulsion system. This result would be beneficial in exploring the roles of biomolecular motor systems in the cellular events that take place at the cell membrane and might also contribute to expanding the nanotechnological applications of biomolecular motors and water-in-oil emulsion systems in the future.

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. The size of a solvophobic part in the amphiphiles dominates the size of an assembling structure; that is, in water, these amphiphiles tethering different lengths of the saccharide part exhibited almost identical assembling size, whereas in chloroform, the size depends on the length of the saccharide part in the amphiphiles.

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. The anisotropic monomer arrangement in the PLMOF underwent axis-dependent crosslinking to yield anisotropically swelling gels. Therefore, the crystal crosslinking of MOFs should be a useful method for creating actuators with designable deformation properties.

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. The CCG showed stimuli-responsive photoluminescence behavior depending on the swelling degree, thus the photoluminescence intensity was higher at higher swelling degree. By changing the solvent, water content, or ionic strength, the photoluminescence intensity was controllable, accompanying the change of swelling degree. Moreover, emission color tuning was also achieved by the introduction of luminescent rare earth ions to form a coordination bonding with residual carboxylate inside the CCG.

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. The addition of the reactant for the "effector", which can interact with the polymer chain for increasing the compatibility of the polymer chain with the media, caused a polymer phase separation, due to reduction of the solvation ability of the effector to the polymer chain. In other words, decrease of the "effector" concentration induced the polymer phase separation. Within our knowledge, this is the first report to connect a polymer phase separation with organic reaction dynamics. This process will be the first step for the development of artificial allosteric enzyme mimics from a combination of a simple synthetic polymer and a product or reactant in organic reactions.

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 = 46.5). The electrostatic repulsion among the polymer chains and the osmotic pressure between the interior and exterior of the MPEgel is responsible for the high swelling ability, revealed by the common ion effect using tetra(n-hexyl)ammonium tetra(3,5-bis(trifluoromethyl)phenylborate (THATFPB). The obtained MPEgels could also absorb liquid crystalline molecules such as 4-cyano-4'-pentylbiphenyl (5CB), analogously caused by the above-mentioned polyelectrolyte characteristic. The MPEgels exhibited liquid crystal transition temperature (TNI) on differential scanning calorimetry (DSC) measurement, and the increase of the ionic group content lowered TNI. The MPEgels absorbing liquid crystalline molecules exhibited differing TNI, dependent on the compatibility of the mesogenic group on the side chain to the liquid crystalline molecule.

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.