A Sandwich-Structured NaTiO/Reduced Graphene Oxide Composite for Improved Energy Storage in Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have the potential to be a cost-effective and sustainable solution for large-scale energy storage systems (ESSs) due to the abundance of sodium reserves. NaTiO has been considered as a suitable candidate for use as an anode material in SIBs owing to its environmental friendliness, low cost, and excellent cycling stability. Despite its advantages, NaTiO has intrinsic limitations such as electrical conductivity.

Au Cluster-Based Atomically Precise Coordination Frameworks and Emission Engineering through Lattice Symmetry.

The atomically precise metal nanoclusters (NCs) have attracted significant attention due to their superatomic behavior originating from the quantum confinement effect. This behavior makes these materials suitable for various photoluminescence-based applications, including chemical sensing, bioimaging, and phototherapy, owing to their intriguing optical properties. Especially, the manipulation of inter- or intracluster interaction through cluster-assembled materials (CAMs) presents significant pathways for modifying the photophysical properties of NCs.

Thermally stable strongly fluorescent multi-stimuli responsive carbazole zwitterionic fluorophores: Alkyl chain length dependent thermofluorochromism and latent fingerprinting.

Carbazole-picoline based π-conjugated zwitterionic fluorophores, (E)-3-(4-(4-(9H-carbazol-9-yl)styryl)pyridin-1-ium-1-yl)propane-1-sulfonate (Cz-PS) and (E)-4-(4-(4-(9H-carbazol-9-yl)styryl)pyridin-1-ium-1-yl)butane-1-sulfonate (Cz-BS) were synthesized and investigated the stimuli-responsive solid-state fluorescence properties. Cz-PS and Cz-BS displayed enhanced fluorescence in the solid-state (555 and 542 nm) with the quantum yield (Φ) of 32.9 and 28.

Amplifying Colossal Thermal Expansion of a Martensitic Molecular Crystal through Interlayer Shear-Induced Side-Chain Liberation.

Molecular crystals capable of colossal thermal expansion (TE) are fascinating owing to their substantial and continuous volume changes and reasonably linear responses to temperature. This makes them promising candidates for micromachine applications. Macroscopic motion is driven by subtle yet cooperative movements of molecules that respond to the thermal motions of dynamic functional units.

Propeller shaped triarylamine acid: An ultra-sensitive fluorescence probe for distinguishing propanol isomers and water sensing in organic solvents.

The photophysical properties of conformationally flexible (TPA-C) and partially rigidified (Cz-C) triarylamine acids were explored in solid as well as solution state and correlated with the structure. TPA-C and Cz-C exhibited moderate solid-state fluorescence (Φ = 6.2 % (TPA-C) and 5.

Controlling Redox Potential of a Manganese(III)-Bis(hydroxo) Complex through Protonation and the Hydrogen-Atom Transfer Reactivity.

A series of mononuclear manganese(III)-hydroxo and -aqua complexes, [Mn(TBDAP)(OH)] (), [Mn(TBDAP)(OH)(OH)] () and [Mn(TBDAP)(OH)] (), were prepared from a manganese(II) precursor and confirmed using various methods including X-ray crystallography. Thermodynamic analysis showed that protonation from hydroxo to aqua species resulted in increased redox potentials () in the order of (-0.15 V) < (0.

Deep blue emitting dual state fluorescent triphenylamine-dicyclohexylurea derivative: Multi-stimuli responsive fluorescence switching and methanol/water sensing.

A new deep blue emissive organic fluorophore (N-cyclohexyl-N-(cyclohexylcarbamoyl)-4-(diphenylamino)benzamide (NCDPB)) was designed and synthesized, which showed strong fluorescence both in solution and solid-state. Solid-state structural analysis of NCDPB revealed non-planar twisted molecular conformation with extended hydrogen bonding between the amide functionalities. The propeller shaped triphenylamine (TPA) and non-planar cyclohexyl unit prevented close π…π stacking and produced strong deep blue emission in the solid state (λ = 400 nm, quantum yield (Φ) = 12.

Radical-Driven Crystal-Amorphous-Crystal Transition of a Metal-Organic Framework.

Self-assembly-based structural transition has been explored for various applications, including molecular machines, sensors, and drug delivery. In this study, we developed new redox-active metal-organic frameworks (MOFs) called DGIST-10 series that comprise π-acidic 1,4,5,8-naphthalenediimide (NDI)-based ligands and Ni ions, aiming to boost ligand-self-assembly-driven structural transition and study the involved mechanism. Notably, during the synthesis of the MOFs, a single-crystal-amorphous-single-crystal structural transition occurred within the MOFs upon radical formation, which was ascribed to the fact that radicals prefer spin-pairing or through-space electron delocalization by π-orbital overlap.

Water sensitive fluorescence tuning of V-shaped ESIPT fluorophores: Substituent effect and trace amount water sensing in DMSO.

Highly sensitive nature of excited state intramolecular proton transfer (ESIPT) functionality in organic fluorophores made them potential candidates for developing environmental sensors and bioimaging applications. Herein, we report the synthesis of V-shaped Dapsone based Schiff base ESIPT derivatives (1-3) and water sensitive wide fluorescence tuning from blue to red in DMSO. Solid-state structural analysis confirmed the V-shaped molecular structure with intramolecular H-bonding and substituent dependent molecular packing in the crystal lattice.

The Effect of Ni Doping on FeOF Cathode Material for High-Performance Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have emerged as a promising alternative to lithium-ion batteries for large-scale energy storage systems due to the abundance and low price of sodium. Until recently, the low theoretical capacities of intercalation-type cathodes less than 250 mAh g have limited the energy density of SIBs. On the other hand, iron oxyfluoride (FeOF) has a high theoretical capacity of ≈885 mAh g as a conversion-type cathode material for SIBs.

Origamic metal-organic framework toward mechanical metamaterial.

Origami, known as paper folding has become a fascinating research topic recently. Origami-inspired materials often establish mechanical properties that are difficult to achieve in conventional materials. However, the materials based on origami tessellation at the molecular level have been significantly underexplored.

Comprehensive Qualitative and Quantitative Colorimetric Sensing of Volatile Organic Compounds Using Monolayered Metal-Organic Framework Films.

Cross-responsive chemical sensors are in high demand owing to their ability to distinguish a broad range of analytes. In this study, a vapochromic sensor array based on metal-organic frameworks (MOFs), which exhibits distinct patterns when exposed to volatile organic compounds (VOCs) and humidity, is developed. Conventional sensor arrays consist of various receptors that produce different responses.

Zn(II)-Siloxane Clusters as Versatile Building Blocks for Carboxylate-Based Metal-Organic Frameworks.

Siloxanes have long been known for their highly desirable properties suited for a wide range of practical applications; however, their utilization as modular building blocks for crystalline open frameworks has been limited. In this study, a simple solvothermal pathway has been found to synthesize unprecedented Zn(II)-siloxane clusters supported by acetate ligands, [(RSiO)Zn(CHCO)] (R = Me or Ph). The same reaction using a dicarboxylate ligand such as 1,4-benzenedicarboxylate or 2,6-naphthalenedicarboxylate produces a new type of metal-organic framework, named SiMOF here, based on the [SiZn] units.

A water coordinated Ni complex and a 2D Ni-MOF: topology dependent highly enhanced electrocatalytic OER activity.

Metal-organic frameworks (MOFs) with their tunable topology, functionality and coordination environment have been considered as potential materials for various applications including electrocatalysis. Herein, we have synthesised a water coordinated nickel based 2D metal-organic framework (Ni-MOF) and a coordination complex (Ni-C) and investigated their electrocatalytic OER activity. The Ni-MOF showed a 2D sheet structure with one water coordination whereas a four water molecule coordinated charged complex was formed in the Ni-C.

Systematic Electronic Tuning on the Property and Reactivity of Cobalt-(Hydro)peroxo Intermediates.

A series of cobalt(III)-peroxo complexes, [Co(R-TBDAP)(O)] (; R = Cl, H, and OMe), and cobalt(III)-hydroperoxo complexes, [Co(R-TBDAP)(OH)(CHCN)] (), bearing electronically tuned tetraazamacrocyclic ligands (R-TBDAP = ,'-di--butyl-2,11-diaza[3.3](2,6)--R-pyridinophane) were prepared from their cobalt(II) precursors and characterized by various physicochemical methods. The X-ray diffraction and spectroscopic analyses unambiguously showed that all compounds have similar octahedral geometry with a side-on peroxocobalt(III) moiety, but the O-O bond lengths of [1.

Carbazole fluorophore with an imidazole/thiazole unit: contrasting stimuli-induced fluorescence switching, water-sensing and deep-blue emission.

Carbazole-based, π-conjugated donor-acceptor fluorophores were synthesized by integrating imidazole/thiazole units. Then, we investigated the impact of subtle structural changes on fluorescence properties. Carbazole integrated with imidazole (Cz-I) and carbazole integrated with thiazole (Cz-T) showed strong fluorescence in solution (quantum yield ( ) = 0.

Highly enhanced electrocatalytic OER activity of water-coordinated copper complexes: effect of lattice water and bridging ligand.

The use of metal-organic compounds as electrocatalysts for water splitting reactions has gained increased attention; however, a fundamental understanding of the structural requirement for effective catalytic activity is still limited. Herein, we synthesized water-coordinated mono and bimetallic copper complexes (CuPz-HO·HO, CuPz-HO, CuBipy-HO·HO, and CuMorph-HO) with varied intermetallic spacing (pyrazine/4,4'-bipyridine) and explored the structure-dependent oxygen evolution reaction (OER) activity in alkaline medium. Single crystal structural studies revealed water-coordinated monometallic complexes (CuMorph-HO) and bimetallic complexes (CuPz-HO·HO, CuPz-HO, CuBipy-HO·HO).

Crystalline hydrogen bonding of water molecules confined in a metal-organic framework.

Hydrogen bonding (H-bonding) of water molecules confined in nanopores is of particular interest because it is expected to exhibit chemical features different from bulk water molecules due to their interaction with the wall lining the pores. Herein, we show a crystalline behavior of H-bonded water molecules residing in the nanocages of a paddlewheel metal-organic framework, providing in situ and ex situ synchrotron single-crystal X-ray diffraction and Raman spectroscopy studies. The crystalline H-bond is demonstrated by proving the vibrational chain connectivity arising between hydrogen bond and paddlewheel Cu-Cu bond in sequentially connected Cu-Cu·····coordinating HO·····H-bonded HO and by proving the spatial ordering of H-bonded water molecules at room temperature, where they are anticipated to be disordered.

High-Throughput Approach for Facile Access to Hetero-Dinuclear Synergistic Metal Complex for HO Activation and Its Implications.

Hetero-dinuclear synergic catalysis is a promising approach for improving catalytic performance. However, employing it is challenging because the design principles for the metal complex are still not well understood. Further, these complexes have a broader set of possibilities than mononuclear or homometallic systems, increasing the time and effort required to understand them.

Methoxy substituent facilitated wide solvatofluorochromism, white light emission, polymorphism and stimuli-responsive fluorescence switching in donor-π-acceptor.

Introducing methoxy substituent into triphenylamine-acetophenone based donor-π-acceptor fluorophore, 3-(4-(diphenylamino)phenyl)-1-phenylprop-2-en-1-one (1), produced strong solvatofluorochromism including white light emission, fluorescent polymorphs and mechano-responsive fluorescence switching. The unsubstituted and methoxy substituted compounds displayed strong solvent polarity mediated tunable emission in the solution. Interestingly, 3-(4-(diphenylamino)phenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (2) and 3-(4-(diphenylamino)-2-methoxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (3) showed single molecule white light emission in DMSO and ethanol, respectively.

Visible-light NO photolysis of ruthenium nitrosyl complexes with NO ligands bearing π-extended rings and their photorelease dynamics.

NO photorelease and its dynamics for two {RuNO} complexes, Ru(salophen)(NO)Cl (1) and Ru(naphophen)(NO)Cl (2), with salen-type ligands bearing π-extended systems (salophenH = ,'-(1,2-phenylene)-bis(salicylideneimine) and naphophenH = ,'-1,2-phenylene-bis(2-hydroxy-1-naphthylmethyleneimine)) were investigated. NO photolysis was performed under white room light and monitored by UV/Vis, EPR, and NMR spectroscopies. NO photolysis was also performed under 459 and 489 nm irradiation for 1 and 2, respectively.

Creating Tunable Mesoporosity by Temperature-Driven Localized Crystallite Agglomeration.

A new synthetic approach for tunable mesoporous metal-organic frameworks (MeMs) is developed. In this approach, mesopores are created in the process of heat conversion of highly mosaic metal-organic framework (MOF) crystals with non-interpenetrated low-density nanocrystallites into MOF crystals with two-fold interpenetrated high-density nanocrystallites. The two-fold interpenetration reduces the volume of the nanocrystallites in the mosaic crystal, and the accompanying localized agglomeration of the nanocrystallites results in the formation of mesopores among the localized crystallite agglomerates.

A functional model for quercetin 2,4-dioxygenase: Geometric and electronic structures and reactivity of a nickel(II) flavonolate complex.

Quercetin 2,4-dioyxgenase (QueD) has been known to catalyze the oxygenative degradation of flavonoids and quercetin. Recent crystallographic study revealed a nickel ion occupies the active site as a co-factor to support O activation and catalysis. Herein, we report a nickel(II) flavonolate complex bearing a tridentate macrocyclic ligand, [Ni(Me-TACN)(Fl)(NO)](HO) (1, Me-TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane, Fl = 3-hydroxyflavone) as a functional model for QueD.

Palladium-Catalyzed Asymmetric Decarboxylative Addition of β-Keto Acids to Heteroatom-Substituted Allenes.

The Pd-catalyzed asymmetric addition reaction of β-keto acids to heteroatom-substituted allene is reported. This reaction generates β-substituted ketones in an asymmetric manner through a branch-selective decarboxylative allylation pathway. The reaction accommodates various alkoxyallenes as well as amidoallenes.