Highly Fluorinated Nanospace in Porous Organic Salts with High Water Stability/Capability and Proton Conductivity.

Water in hydrophobic nanospaces shows specific dynamic properties different from bulk water. The investigation of these properties is important in various research fields, including materials science, chemistry, and biology. The elucidation of the correlation between properties of water and hydrophobic nanospaces requires nanospaces covered only with simple hydrophobic group (e.g., fluorine) without impurities such as metals. This work successfully fabricated all-organic diamondoid porous organic salts (d-POSs) with highly fluorinated nanospaces, wherein hydrophobic fluorine atoms are densely exposed on the void surfaces, by combining fluorine substituted triphenylmethylamine (TPMA) derivatives with tetrahedral tetrasulfonic acid. This d-POSs with a highly fluorinated nanospace significantly improved their water stability, retaining their crystal structure even when immersed in water over one week. Moreover, this highly hydrophobic and fluorinated nanospace adsorbs 160 mL(STP)/g of water vapor at Pe/P0 = 0.90; this is the first hydrophobic nanospace, which water molecules can enter, in an all-organic porous material. Furthermore, this highly fluorinated nanospace exhibits very high proton conductivity (1.34 × 10-2 S/cm) at 90°C and 95%RH. POSs with tailorable nanospaces may significantly advance the elucidation of the properties of specific "water" in pure hydrophobic environments.

Unlocking the Charge-storage Potential of a Phenanthraquinone-based Two-dimensional Covalent Organic Framework (2D COF).

The high surface area, open pore-structure and atomic-level organization inherent in many covalent organic frameworks (COFs) make them an attractive polymer platform for developing functional materials. Herein, a chemically robust 2D COF (TpOMe-DAPQ COF) containing phenanthraquinone moieties was prepared by condensing 2,4,6-trimethoxy-1,3,5-benzenetricarbaldehyde (TpOMe) and 2,7-diamino-9,10-phenanthraquinone (DAPQ) using the convenient mechanochemical method. The poor charge-storage capacity of the pristine TpOMe-DAPQ COF was substantially improved by first investigating its redox-site accessibility (RSA) using different conductivity-enhancement methods, and then optimizing the amount of EDOT needed to perform an in-situ polymerization. The resulting composite (0.4EDOT@TpOMe-DAPQ) was characterized and its enhanced charge-storage capabilities enabled it to be used as an anode material in an aqueous Mn beaker-cell battery capable of delivering 0.76 V. This work outlines the rational design approach used to develop a functional charge-storage material utilizing a COF-based polymerization platform.

Anticancer nano-prodrugs with drug release triggered by intracellular dissolution and hydrogen peroxide response.

We developed prodrug nanoparticles that release drugs through intracellular dissolution and a cancer-specific hydrogen peroxide response. To reveal the unclear mechanism regarding drug release from nanoparticles by reacting with hydrogen peroxide in cancer cells, this study demonstrates the in vitro evaluation of drug release kinetics under conditions simulated in cancer cells.

Network topology diversification of porous organic salts.

Hydrogen-bonded organic frameworks (HOFs) are porous organic materials constructed via hydrogen bonds. HOFs have solubility in specific high-polar organic solvents. Therefore, HOFs can be returned to their components and can be reconstructed, which indicates their high recyclability. Network topologies, which are the frameworks of porous structures, control the pore sizes and shapes of HOFs. Therefore, they strongly affect the functions of porous materials. However, hydrogen bonds are usually weak interactions, and the design of the intended network topology in HOFs from their components has been challenging. Porous organic salts (POSs) are an important class of HOFs, are hierarchically constructed via strong charge-assisted hydrogen bonds between sulfonic acids and amines, and therefore are expected to have high designability of the porous structure. However, the network topology of POSs has been limited to only dia-topology. Here, we combined tetrasulfonic acid with the adamantane core (4,4',4'',4'''-(adamantane-1,3,5,7-tetrayl)tetrabenzenesulfonic acid; AdPS) and triphenylmethylamines with modified substituents in para-positions of benzene rings (TPMA-X, X = F, methyl (Me), Cl, Br, I). We changed the steric hindrance between the adamantane and substituents (X) in TPMA-X and obtained not only the common dia-topology for POSs but also rare sod-topology, and lon- and uni-topologies that are formed for the first time in HOFs. Changing template molecules under preparation helped in successfully isolating the porous structures of AdPS/TPMA-Me with dia-, lon-, and sod-topologies which exhibited different gas adsorption properties. Therefore, for the first time, we demonstrated that the steric design of HOF components facilitated the formation, diversification, and control of the network topologies and functions of HOFs.

Breathing Metal-Organic Frameworks Supported by an Arsenic-Bridged 4,4'-Bipyridine Ligand.

Bent ligands bridged by heteroatoms have drawn significant interest as supramolecular coordination architectures. Traditionally, divalent group 16 elements are preferred over trivalent group 15 elements because of the anticipated steric hindrance. In this study, we explore metal-organic frameworks (MOFs) based on dipyridinoarsoles (DPAs), 4,4'-bipyridines bridged with an arsenic atom. An MOF with methyl-substituted DPA collapsed upon solvent removal, whereas that with phenyl-substituted DPA demonstrated breathing behavior due to guest molecule adsorption/desorption. In contrast, MOFs using the phosphorus analogue dipyridinophosphole exhibit inferior adsorption and lack breathing behavior. This is the first study to investigate the interplay among substituents, bridging elements, and dynamic behavior in MOFs using bent group 15 ligands.

Ice-Like Dynamics of Water Clusters.

Understanding certain behaviors of water, e.g., its dynamics, is extremely important in various fields. Recently, using 1H nuclear magnetic resonance spectroscopy, we have identified a metastable state of water molecules, i.e., water clusters, in hydrophobic solvents in addition to dissolved water molecules and a small bulk water domain. However, the low abundance of water clusters made observing their dynamics challenging. In this study, the dynamics of water clusters in benzene-d6 were investigated by quasi-elastic neutron scattering measurements using the AGNES time-of-flight spectrometer of the Japan Research Reactor JRR-3. The diffusion dynamics of the hydrogen atoms were much slower than those of bulk water (with a self-diffusion coefficient of 1.15 × 10-9 m2/s at 273 K) and even slower than the upper-limit dynamics at the observable scale (10-10 m2/s). The dynamics of water clusters are slow, "like ice", even at 283-303 K, which is above the freezing point of water (273 K).

Spirobifluorene-Based Porous Organic Salts: Their Porous Network Diversification and Construction of Chiral Helical Luminescent Structures.

Porous organic salts (POSs) are organic porous materials assembled via charge-assisted hydrogen bonds between strong acids and bases such as sulfonic acids and amines. To diversify the network topology of POSs and extend its functions, this study focused on using 4,4',4'',4'''-(9,9'-spirobi[fluorene]-2,2',7,7'-tetrayl)tetrabenzenesulfonic acid (spiroBPS), which is a tetrasulfonic acid comprising a square planar skeleton. The POS consisting of spiroBPS and triphenylmethylamine (TPMA) (spiroBPS/TPMA) was constructed from the two-fold interpenetration of an orthogonal network with pts topology, which has not been reported in conventional POSs, owing to the shape of the spirobifluorene backbone. Furthermore, combining tris(4-chlorophenyl)methylamine (TPMA-Cl) and tris(4-bromophenyl)methylamine (TPMA-Br), which are bulkier than TPMA owing to the introduction of halogens at the p-position of the phenyl groups with spiroBPS allows us to construct novel POSs (spiroBPS/TPMA-Cl and spiroBPS/TPMA-Br). These POSs were constructed from a chiral helical network with pth topology, which was induced by the steric hindrance between the halogens and the curved fluorene skeleton. Moreover, spiroBPS/TPMA-Cl with pth topology exhibited circularly polarized luminescence (CPL) in the solid state, which has not been reported in hydrogen-bonded organic frameworks (HOFs).

Control of Relative Positions of Electron-Donor and Electron-Acceptor Molecules in Charge-Transfer Complexes for Luminescent Property Modulation.

Charge-transfer complexes can exhibit various physical properties that depend on the relative positions of electron-donor and electron-acceptor molecules. Several studies have investigated the relationship between the relative positions of electron-donor and electron-acceptor molecules and their luminescence properties. However, elucidating the correlation between the relative positions and detailed luminescence processes without changing the molecular structures has not been explored. Herein, we report control of the relative position based on charge-assisted hydrogen bonds between sulfo and amino groups and on alkylamines' steric factors, and report concomitant modulation of the luminescent properties. Six charge-transfer complexes were prepared from anthracene-2,6-disulfonic acid and 1,2,4,5-tetracyanobenzene as electron-donor and electron-acceptor molecules, and various alkylamines. Different alkylamines' steric factors drastically and precisely changed the relative positions of the electron-donor and electron-acceptor molecules without changing their molecular structures. Consequently, the six crystals exhibited maximum emission wavelengths from 543 to 624 nm and different luminescence processes.

Design of a robust and strong-acid MOF platform for selective ammonium recovery and proton conductivity.

Metal-organic frameworks (MOFs) are potential candidates for the platform of the solid acid; however, no MOF has been reported that has both aqueous ammonium stability and a strong acid site. This manuscript reports a highly stable MOF with a cation exchange site synthesized by the reaction between zirconium and mellitic acid under a high concentration of ammonium cations (NH4+). Single-crystal XRD analysis of the MOF revealed the presence of four free carboxyl groups of the mellitic acid ligand, and the high first association constant (pKa1) of one of the carboxyl groups acts as a monovalent ion-exchanging site. NH4+ in the MOF can be reversibly exchanged with proton (H+), sodium (Na+), and potassium (K+) cations in an aqueous solution. Moreover, the uniform nanospace of the MOF provides the acid site for selective NH4+ recovery from the aqueous mixture of NH4+ and Na+, which could solve the global nitrogen cycle problem. The solid acid nature of the MOF also results in the proton conductivity reaching 1.34 × 10-3 S cm-1 at 55 °C by ion exchange from NH4+ to H+.

Accelerated Oxidative Degradation of Phosphonium-Type Ionic Liquid with l-Prolinate Anion: Degradation Mechanism and CO2 Separation Performance.

Amino acid ionic liquids (AAILs) are regarded as green alternatives to existing CO2-sorptive materials because amino acids are readily available from renewable sources in large quantities. For widespread applications of AAILs, including direct air capture, the relationship between the stability of AAILs, especially toward O2, and the CO2 separation performance is of particular importance. In the present study, the accelerated oxidative degradation of tetra-n-butylphosphonium l-prolinate ([P4444][Pro]), a model AAIL that has been widely investigated as a CO2-chemsorptive IL, is performed using a flow-type reactor system. Upon heating at 120-150 °C and O2 gas bubbling to [P4444][Pro], both the cationic and anionic parts undergo oxidative degradation. The kinetic evaluation of the oxidative degradation of [P4444][Pro] is performed by tracing the decrease in the [Pro]- concentration. Supported IL membranes composed of degraded [P4444][Pro] are fabricated, and the membranes retain CO2 permeability and CO2/N2 selectivity values in spite of the partial degradation of [P4444][Pro].

All-Solid-State Rechargeable Air Batteries Using Dihydroxybenzoquinone and Its Polymer as the Negative Electrode.

A proof-of-concept study was conducted on an all-solid-state rechargeable air battery (SSAB) using redox-active 2,5-dihydroxy-1,4-benzoquinone (DHBQ) and its polymer (PDBM) and a proton-conductive polymer (Nafion). DHBQ functioned well in the redox reaction with the solid Nafion ionomer at 0.47 and 0.57 V vs. RHE, similar to that in acid aqueous solution. The resulting air battery exhibited an open circuit voltage of 0.80 V and a discharge capacity of 29.7 mAh gDHBQ -1 at a constant current density (1 mA cm-2 ). With PDBM, the discharge capacity was much higher, 176.1 mAh gPDBM -1 , because of the improved utilization of the redox-active moieties. In the rate characteristics of the SSAB-PDBM, the coulombic efficiency was 84 % at 4 C, which decreased to 66 % at 101 C. In a charge/discharge cycle test, the capacity remaining after 30 cycles was 44 %, which was able to be significantly improved, to 78 %, by tuning the Nafion composition in the negative electrode.

Statically and dynamically flexible hydrogen-bonded frameworks based on 4,5,9,10-tetrakis(4-carboxyphenyl)pyrene.

Aperture shape and size of flexible hydrogen-bonded organic frameworks (HOF) were statically modulated using various aromatic solvents, and dynamically changed by desorption and adsorption of the solvent molecules.

Precise Control of the Molecular Arrangement of Organic Semiconductors for High Charge Carrier Mobility.

Organic semiconductors are well-known to exhibit high charge carrier mobility based on their spread of the π-orbital. In particular, the π-orbital overlap between neighboring molecules significantly affects their charge carrier mobility. This study elucidated the direct effect of subtle differences in the π-orbital overlap on charge carrier mobility, by precisely controlling only molecular arrangements without any chemical modifications. We synthesized disulfonic acid composed of a [1]benzothieno[3,2-b][1]benzothiophene (BTBT) moiety, and prepared organic salts with four butylamine isomers. Regardless of the type of butylamine combined, electronic states of the constituent BTBT derivative were identical, and all BTBT arrangements were edge-to-face herringbone-type. However, depending on the difference of steric hindrance, center-to-center distances and dihedral angles between neighboring BTBT moieties slightly varied. Despite a similar arrangement, the photoconductivity of four organic salts differed by a factor of approximately two. Additionally, theoretical charge carrier mobilities from their crystal structures exhibited a strong correlation with their photoconductivity.

Cage-Like Sodalite-Type Porous Organic Salts Enabling Luminescent Molecule's Incorporation and Room-temperature Phosphorescence Induction in Air.

Expression of room-temperature phosphorescence (RTP) in organic materials requires complicated molecular design and specific intermolecular interactions, and therefore types of RTP materials are restricted. This work presents cage-like sodalite-type porous organic salts (s-POSs) as host materials for luminescent molecules to induce RTP, using tetrasulfonic acid with an adamantane core and triphenylmethylamines that are modified with substituents in the para-positions of benzene rings (TPMA-X). By adding a representative luminescent molecule (pyrene) to a reaction solution during construction of s-POSs, the molecule is incorporated in a facile manner. s-POSs with a heavy halogen atom (X: Iodine) on the pore surface give heavy atom effects, suppression of thermal vibration, and protection from oxygen, for the incorporated molecule, which induce its RTP even in air. This strategy can be applied to various luminescent molecules, which may lead to the achievement of RTP of various colors.

3,11-Diaminodibenzo[a,j]phenazine: Synthesis, Properties, and Applications to Tröger's Base-Forming Ladder Polymerization.

A new class of diamino-substituted π-extended phenazine compound was synthesized, and its photophysical properties were investigated. The U-shaped diaminophenazine displayed photoluminescence in solution with moderate quantum yield. The diamino aromatic compound was found applicable to the poly-condensation with formaldehyde to form Tröger's base ladder polymer. The obtained microporous ladder polymer features high CO2 adsorption selectivity against N2 , most likely due to the presence of basic nitrogen atoms in the phenazine rings.

Tetrachlorocatecholates of triarylarsines as a novel class of Lewis acids.

Pnictogen-mediated Lewis acidity is an emerging research subject in organic chemistry, supramolecular chemistry, etc. In contrast to the extensive studies on phosphorus and antimony, the diversity of arsenic-Lewis acids was quite limited. Herein, tetrachlorocatecholates of triarylarsines were newly synthesized. Their structures, electronic properties, and Lewis acidities were experimentally and computationally examined and compared with the corresponding phosphorus and antimony analogs. This is the first systematic study on the relationship between the structure and Lewis acidity of arsenic-mediated Lewis acids.

Systematic Study of Pnictogen-Fused Heterofluorenes.

Heteroatom-fused π-conjugated molecules have attracted considerable attention, and various elements for such fusion have been investigated. Herein, we focused on pnictogen-fused heterofluorenes. The structures, reactivity with O2 and I2, coordination ability to AuCl, and photophysical properties were systematically studied to better understand the effects of pnictogen atoms on the nature of π-conjugated molecules.

Porous Organic Salts: Diversifying Void Structures and Environments.

Porous organic salts (POSs) are porous organic materials, in which various aromatic sulfonic acids and amines are regularly self-assembled by charge-assisted hydrogen bonding. POSs exhibit high solubility in highly polar solvents. Therefore, they are prepared via facile recrystallization and exhibit high recyclability. In this study, tetrahedral-structured tetrasulfonic acid and triphenylmethylamine (TPMA) were combined to construct POSs with rigid diamond networks called diamondoid porous organic salts (d-POSs). Furthermore, by introducing substituents (e.g., F, Cl, Br, or I) at the para-positions of benzene rings of TPMA, these substituents were exposed on the void surface of d-POSs, and their diamond networks were distorted. This induced the formation of a variety of void structures and environments in the d-POSs, which significantly affected their gas adsorption behavior. In particular, the d-POS from TPMA substituted by fluorine exhibited very high CO2 adsorption of 182 mL(STP) g-1 at 1 atm in all-organic porous materials.

Two States of Water Converge to One State below 215 K.

Anomalies of water have been explained by the two-state water model. In the model, water becomes one state upon supercooling. However, water crystallizes completely below 235 K ("no man's land"). The structural origin of the anomalous of the water is hidden in the "no man's land". To understand the properties of water, the spectroscopic experiment in "Norman's land" is inevitable. Hence, we proposed a new soft-confinement method for standard nuclear magnetic resonance spectroscopy to explore the "no man's land". We found the singularity temperature (215 K) at ambient pressure. Water exists in one state below 215 K. Above 215 K, the two states of water are supercritical states of the liquid-liquid critical point. The current study provides a perspective to determine the liquid-liquid critical point of water existing in a high-pressure condition.

Copolymer of Phenylene and Thiophene toward a Visible-Light-Driven Photocatalytic Oxygen Reduction to Hydrogen Peroxide.

π-Conjugated polymers including polythiophenes are emerging as promising electrode materials for (photo)electrochemical reactions, such as water reduction to H2 production and oxygen (O2) reduction to hydrogen peroxide (H2O2) production. In the current work, a copolymer of phenylene and thiophene is designed, where the phenylene ring lowers the highest occupied molecular orbital level of the polymer of visible-light-harvesting thiophene entities and works as a robust catalytic site for the O2 reduction to H2O2 production. The very high onset potential of the copolymer for O2 reduction (+1.53 V vs RHE, pH 12) allows a H2O2 production setup with a traditional water-oxidation catalyst, manganese oxide (MnO x ), as the anode. MnO x is deposited on one face of a conducting plate, and visible-light illumination of the copolymer layer formed on the other face aids steady O2 reduction to H2O2 with no bias assistance and a complete photocatalytic conversion rate of 14 000 mg (H2O2) gphotocat -1 h-1 or ≈0.2 mg (H2O2) cm-2 h-1.