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 (λmax = 400 nm, quantum yield (Φf) = 12.6 %). NCDPB also exhibited strong solvent polarity dependent tunable emission in solution (λmax = 402-462 nm, Φf = 1.15 (compared to quinine sulphate)). NCDPB showed reversible fluorescence switching between two fluorescence states upon mechanical crushing and heating/solvent exposure. Mechanical crushing caused red shifting of fluorescence from 400 to 447 nm and heating/solvent exposure reversed the fluorescence. Further, NCDPB also displayed off-on reversible/self-reversible fluorescence switching upon exposure to trifluoracetic acid (TFA) and NH3. The repeated fluorescence switching cycles indicated high reversibility without any significant change of fluorescence intensity. The drastically different fluorescence of NCDPB in CH3OH and EtOH was utilized to distinguish them and monitor CH3OH contamination in ethanol and benzene. It showed limit of detection (LOD) of methanol up to 0.25 % and 7 % in benzene and ethanol, respectively. The water sensitive fluorescence modulation of NCDPB in organic solvents was used to sensing water contamination in common organic solvents. Thus, integration of twisted TPA with H-bonding urea produced dual state emitting organic fluorophore with multi-responsive fluorescence switching and solvent sensing.

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 Ni2+ 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. The radical-formation-induced structural transitions were further confirmed by the postsynthetic solvothermal treatment of isolated nonradical MOF crystals. Notably, the transient amorphous phase without morphological disintegration was clearly observed, contributing to the seminal structural change of the MOF. We believe that this unprecedented structural transition triggered by the ligand self-assembly magnifies the structural flexibility and diversity of MOFs, which is one of the pivotal aspects of MOFs.

Solvent-induced structural transformation in a one-dimensional coordination polymer.

We have rationally designed a one-dimensional coordination polymer (1D CP), termed 1D-DGIST-18, that exhibits intrinsic structural flexibility. This 1D CP enables its expansion into a three-dimensional network through supramolecular interactions involving coordinated solvents and/or ligands. The strategic selection of solvents for solvent exchange, prior to drying, significantly influences the structures of 1D-DGIST-18 by removing certain coordinating solvents and modulating π-π stacking. Consequently, a hierarchical porosity emerges, ranging from micro- to meso- to macroporous structures, which is attributed to its inherent structural dynamics. Additionally, the formation of excimers endows 1D-DGIST-18, when immersed in acetone, with 'turn-on' fluorescence, as evidenced by fluorescence decay profiles. These structural transitions within 1D-DGIST-18 are further elucidated using single-crystal X-ray diffractometry. The insights from this study provide a foundation for the design of materials with structural dynamics and tunable properties.

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. 1 showed strong solid-state fluorescence (λmax = 554 nm, Φf = 21.2 %) whereas methoxy substitution (2 and 3) produced tunable but significantly reduced fluorescence (λmax = 547 (2) and 615 nm (3), Φf = 2.1 (2) and 6.5 % (3)). Interestingly, aggregation induced emission (AIE) studies in DMSO-water mixture revealed water sensitive fluorescence tuning. The trace amount of water (less than 1 %) in DMSO converted the non-emissive 1-3 into highly emissive state due to keto tautomer formation. Further increasing water percentage produced deprotonated state of 1-3 in DMSO and enhanced the fluorescence intensity with red shifting of emission peak. At higher water fraction, 1-3 in DMSO produced aggregates and red shifted the emission with reduction of fluorescence intensity. The concentration dependent fluorescence study revealed the very low detection limit of water in DMSO. The limit of detection (LOD) of 1, 2 and 3 were 0.14, 1.04 and 0.65 % of water in DMSO. Hence, simple Schiff bases of 1-3 showed water concentration dependent keto isomer, deprotonated and aggregated state tunable fluorescence in DMSO. Further, scanning electron microscopic (SEM) studies of 1-3 showed water concentration controlled self-assembly and tunable fluorescence.

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. The vapochromic MOF-based sensor comprises dicopper paddlewheel clusters and dimethylamine azobenzene as binary colorimetric sensing moieties. Upon exposure to VOCs, the constructed sensor encompasses a broad spectrum of colors, ranging from green to red. Furthermore, the color of the MOF is influenced by the solvent used during the pretreatment. Consequently, monolayered MOF thin films can be adapted to multicomponent array systems by immersing the MOF in different solvents. This system provides both qualitative and quantitative sensing, generating unique color patterns corresponding to specific VOC types. Notably, the sensor successfully discriminates each of 14 common VOCs and water and accurately categorizes unknown samples. Moreover, the system undergoes reversible color changes in response to humidity, obviating the need for high-temperature regeneration steps. This novel approach offers insights into the versatile applications of MOFs by creating a colorimetric sensor array capable of detecting various analytes.

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. Herein, we report a two-dimensional (2D) porphyrinic metal-organic framework (MOF), self-assembled from Zn nodes and flexible porphyrin linkers, displaying folding motions based on origami tessellation. A combined experimental and theoretical investigation demonstrated the origami mechanism of the 2D porphyrinic MOF, whereby the flexible linker acts as a pivoting point. The discovery of the 2D tessellation hidden in the 2D MOF unveils origami mechanics at the molecular level.

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-1 have limited the energy density of SIBs. On the other hand, iron oxyfluoride (FeOF) has a high theoretical capacity of ≈885 mAh g-1 as a conversion-type cathode material for SIBs. However, FeOF suffers from poor cycling stability, rate capability, and low initial Coulombic efficiency caused by its low electrical conductivity and slow ionic diffusion kinetics. To solve these problems, doping aliovalent Ni2+ on FeOF electrodes is attempted to improve the electronic conductivity without using a carbon matrix. The ionic conductivity of FeOF is also enhanced due to the formation of oxygen defects in the FeOF crystal structure. The FeOF-Ni1 electrode shows an excellent cycling performance with a reversible discharge capacity of 450.4 mAh g-1 at 100 mAh g-1 after 100 cycles with a fading rate of 0.20% per cycle. In addition, the FeOF-Ni1//hard carbon full cell exhibited a high energy density of 876.9 Wh kg-1 cathode with a good cycling stability.

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, [(RSiO2)8Zn8(CH3CO2)8] (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 [Si8Zn8] units. With the maximum connectivity of 8, the building block is shown to form topologically interesting structures such as octahedral supercages or uninodal 8-connected frameworks. All SiMOFs synthesized possess permanent porosity and high thermal stability and are naturally hydrophobic, as demonstrated by adsorptions of toluene, ethanol, methanol, and water vapor as well as water contact angle measurements. These promising characteristics for well-defined porous solids are attributed to metal-bound siloxane groups in the structural building 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. Thermogravimetric analysis (TGA) confirmed their water coordination and good thermal stability. Interestingly, electrocatalytic OER studies showed strongly enhanced activity for the Ni-MOF and that it required a low overpotential (194 mV) to produce a geometric current density of 10 mA cm-2. The Ni-C required 225 mV to produce 10 mA cm-2. The post-catalytic analysis suggested that the Ni-MOF and Ni-C are converted to nickel hydroxides/oxyhydroxides during electrocatalysis and acted as the catalytic centre. The low Tafel slope and charge transfer resistance further supported the higher activity of Ni-MOF based nickel hydroxides/oxyhydroxides. Chronoamperometric studies revealed the excellent stability of the Ni-MOF based catalyst over 72 h. The present study revealed the potential of developing highly active electrocatalysts based on Ni-MOFs by optimizing the topology and coordination environment.

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

A series of cobalt(III)-peroxo complexes, [CoIII(R2-TBDAP)(O2)]+ (1R2; R2 = Cl, H, and OMe), and cobalt(III)-hydroperoxo complexes, [CoIII(R2-TBDAP)(O2H)(CH3CN)]2+ (2R2), bearing electronically tuned tetraazamacrocyclic ligands (R2-TBDAP = N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)-p-R2-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 1R2 compounds have similar octahedral geometry with a side-on peroxocobalt(III) moiety, but the O-O bond lengths of 1Cl [1.398(3) Å] and 1OMe [1.401(4) Å] were shorter than that of 1H [1.456(3) Å] due to the different spin states. For 2R2, the O-O bond vibration energies of 2Cl and 2OMe were identical at 853 cm-1 (856 cm-1 for 2H), but their Co-O bond vibration frequencies were observed at 572 cm-1 for 2Cl and 550 cm-1 for 2OMe, respectively, by resonance Raman spectroscopy (560 cm-1 for 2H). Interestingly, the redox potentials (E1/2) of 2R2 increased in the order of 2OMe (0.19 V) < 2H (0.24 V) < 2Cl (0.34 V) according to the electron richness of the R2-TBDAP ligands, but the oxygen-atom-transfer reactivities of 2R2 showed a reverse trend (k2: 2Cl < 2H < 2OMe) with a 13-fold rate enhancement at 2OMe over 2Cl in a sulfoxidation reaction with thioanisole. Although the reactivity trend contradicts the general consideration that electron-rich metal-oxygen species with low E1/2 values have sluggish electrophilic reactivity, this could be explained by a weak Co-O bond vibration of 2OMe in the unusual reaction pathway. These results provide considerable insight into the electronic nature-reactivity relationship of metal-oxygen species.

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 (Φ f) = 0.18 (Cz-I) and 0.14 (Cz-T) compared with the standard quinine sulfate) and solid-state (Φ f = 8.0% (Cz-I) and 14.6% (Cz-T)). Cz-I showed relatively more blue-shifted emission in solution compared with the solid-state (λ max = 417 nm (CH3CN) and 460 nm (solid)). Cz-T exhibited deep-blue emission in the solid-state compared with solution (λ max = 455 nm (CH3CN) and 418 nm (solid)). Interestingly, Cz-T exhibited a drastic change in fluorescence in organic solvents (CH3CN, THF, CH3OH, DMSO) with a low percentage (1%) of water. Cz-I showed reversible fluorescence switching between two fluorescence states upon exposure to trifluoracetic acid (TFA)/ammonia (NH3). In contrast, Cz-T displayed reversible/self-reversible off-on fluorescence switching upon exposure to TFA or NH3. Mechanofluorochromic studies of Cz-I showed a slight reduction in fluorescence intensity upon crushing and reversal to the initial state upon heating. Cz-T exhibited off-on reversible/self-reversible fluorescence switching upon crushing/heating. Computational studies indicated that thiazole integration improved the electron-withdrawing characteristics compared with imidazole and contributed to contrasting fluorescence responses. Thus, a simple change of nitrogen with sulfur produced contrasting self-assembly in the solid-state that led to different functional properties and stimuli-induced fluorescence switching.

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-H2O·H2O, CuPz-H2O, CuBipy-H2O·H2O, and CuMorph-H2O) 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-H2O) and bimetallic complexes (CuPz-H2O·H2O, CuPz-H2O, CuBipy-H2O·H2O). Further, CuPz-H2O·H2O and CuBipy-H2O·H2O contained lattice water along with coordinated water. Interestingly, the bimetallic copper complex with lattice water and shorter interspacing between the metal centres (CuPz-H2O·H2O) showed strong OER activity and required an overpotential of 228 mV to produce a benchmark current density of 10 mA cm-2. Bimetallic copper complex (CuPz-H2O) without lattice water but the same intermetallic spacing and bimetallic complex with increased interspacing but with lattice water (CuBipy-H2O·H2O) exhibited relatively lower OER activity. CuPz-H2O and CuBipy-H2O·H2O required an overpotential of 236 and 256 mA cm-2, respectively. Monometallic CuMorph-H2O showed the lowest OER activity (overpotential 271 mV) compared to bimetallic complexes. The low Tafel slope and charge transfer resistance of CuPz-H2O·H2O facilitated faster charge transfer kinetics at the electrode surface and supported the enhanced OER activity. The chronoamperometric studies indicated good stability of the catalyst. Overall, the present structure-electrocatalytic activity studies of copper complexes might provide structural insight for designing new efficient electrocatalysts based on metal coordination compounds.

High-Throughput Approach for Facile Access to Hetero-Dinuclear Synergistic Metal Complex for H2O2 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. In this study, we explored a high-throughput approach to obtain a new hetero-dinuclear synergistic metal complex for H2O2 activation. From the 1152 combinations of metal complex candidates obtained by changing three variables (metal ions, unsymmetrical dinucleating ligands, and pH), the lead complex (L3-(Ni, Co)), which has the highest peroxidase activity, was derived using colorimetric parallel analysis. A series of control experiments revealed that L3 plays a crucial role in the formation of active L3-(Ni, Co) complexes, Co2+ acts as a catalytic center, and Ni2+ serves as an assistant catalytic site within L3-(Ni, Co). In addition, the catalytic efficiency of L3-(Ni, Co), which was 125 times that of the homo-bimetallic complex (L3-(Co, Co)), revealed clear hetero-bimetallic synergism in the buffer. The ultraviolet-visible study and electron paramagnetic resonance-based spin-trap experiment provided mechanistic insight into H2O2 activation by the intermediate, which was found to be induced by the reaction of L3-(Ni, Co) and H2O2. Moreover, the intermediate could act as a donor of the hydroperoxyl radical (•OOH) in the buffer. Furthermore, L3-(Ni, Co) demonstrated potential for application as a signal transducer for H2O2 in an enzyme-coupled cascade assay that can be used for the colorimetric detection of glucose.

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. 1-3 exhibited strong green/yellow fluorescence in the solid-state (Quantum yield (Φf) = 10 to 23%). 2 produced fluorescent polymorphs (green (2-G) and yellow (2-Y). Single crystal structural analysis revealed that donor and acceptor phenyl units adopted coplanar conformation in 2-G and 3 whereas twisted molecular conformation in 1 and 2-Y. Further, 2-G exhibited π…π interactions facilitated isolated dimers whereas 2-Y showed well separated molecules in the crystal lattice. Aggregation induced emission (AIE) studies showed morphological transformation induced fluorescence tuning for 2. The intramolecular charge transfer (ICT) from TPA to acetophenone was confirmed by computational studies. Mechanofluorochromic (MFC) studies of 1 showed only slight reduction of intensity without modulating fluorescence wavelength significantly but 2 and 3 exhibited visible emissive colour change from yellow to green and vice versa by crushing and heating. Both 2 and 3 also exhibited self-reversible fluorescence switching that was confirmed by PXRD pattern. Thus, methoxy group introduction resulted in obtaining white light emitting fluorescence molecules in the solution state and self-reversible fluorescence switching materials.

Visible-light NO photolysis of ruthenium nitrosyl complexes with N2O2 ligands bearing π-extended rings and their photorelease dynamics.

NO photorelease and its dynamics for two {RuNO}6 complexes, Ru(salophen)(NO)Cl (1) and Ru(naphophen)(NO)Cl (2), with salen-type ligands bearing π-extended systems (salophenH2 = N,N'-(1,2-phenylene)-bis(salicylideneimine) and naphophenH2 = N,N'-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. The photochemical quantum yields of the NO photolysis (ΦNO) of both 1 and 2 were determined to be 9% at the irradiation wavelengths. The structural and spectroscopic characteristics of the complexes before and after the photolysis confirmed the conversion of diamagnetic Ru(II)(L)(Cl)-NO+ to paramagnetic S = ½ Ru(III)(L)(Cl)-solvent by photons (L = salophen2- and naphophen2-). The photoreleased NO radicals were detected by spin-trapping EPR. DFT and TDDFT calculations found that the photoactive bands are configured as mostly the ligand-to-ligand charge transfer (LLCT) of π(L) → π*(Ru-NO), suggesting that the NO photorelease was initiated by the LLCT. Dynamics of NO photorelease from the complexes in DMSO under 320 nm excitation were investigated by femtosecond (fs) time-resolved mid-IR spectroscopy. The primary photorelease of NO occurred for less than 0.32 ps after the excitation. The rate constants (k-1) of the geminate rebinding of NO to the photolyzed 1 and 2 were determined to be (15 ps)-1 and (13 ps)-1, respectively. The photochemical quantum yields of NO photolysis (ΦNO, λ = 320 nm) were estimated to be no higher than 14% for 1 and 11% for 2, based on the analysis of the fs time-resolved IR data. The results of fs time-resolved IR spectroscopy and theoretical calculations provided some insight into the overall kinetic reaction pathway, localized electron pathway or resonance pathway, of the NO photolysis of 1 and 2. Overall, our study found that the investigated {RuNO}6 complexes, 1 and 2, with planar N2O2 ligands bearing π-extended rings effectively released NO under visible light.

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. The pore size can be easily modulated from 7 to 90 nm by controlling the heat treatment conditions, that is, the aging temperature and aging time. Various proteins can be encapsulated in the MeM, and immobilized enzymes show catalyst activity comparable to that of the free native enzymes. Immobilized ß-galactosidase is recyclable and the enzyme activity of the immobilized catalase is maintained after exposure to high temperatures and various organic solvents.

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 O2 activation and catalysis. Herein, we report a nickel(II) flavonolate complex bearing a tridentate macrocyclic ligand, [NiII(Me3-TACN)(Fl)(NO3)](H2O) (1, Me3-TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane, Fl = 3-hydroxyflavone) as a functional model for QueD. The flavonolatonickel(II) complex was characterized by using spectrometric analysis including UV-vis spectroscopy, electrospray ionization mass spectrometer (ESI-MS), infrared spectroscopy (FT-IR) and 1H nuclear magnetic resonance spectroscopy (NMR). The single crystal X-ray structure of 1 shows two isomers with respect to the direction of a flavonolate ligand. Two isomers commonly are in the octahedral geometry with a bidentate of flavonolate and a monodentate of nitrate as well as a tridentate binding of Me3-TACN ligand. The spin state of 1 is determined to be a triplet state based on the Evans' method. Interestingly, electronic configuration of 1 from density functional theory (DFT) calculations revealed that the two singly occupied molecular orbitals (SOMOs) lie energetically lower than the highest (doubly) occupied molecular orbital (HOMO), that is so-called the SOMO-HOMO level inversion (SHI). The HOMO shows an electron density localized in the flavonolate ligand, indicating that flavonolate ligand is oxidized first rather than the nickel center. Thermal degradation of 1 resulted in the formation of benzoic acid and salicylic acid, which is attributed to the oxygenation of flavonolate of 1.

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 H2O·····H-bonded H2O and by proving the spatial ordering of H-bonded water molecules at room temperature, where they are anticipated to be disordered. Additionally, we show a substantial distortion of the paddlewheel Cu2+-centers that arises with water coordination simultaneously. Also, we suggest the dynamic coordination bond character of the H-bond of the confined water, by which an H-bond transitions to a coordination-bond at the Cu2+-center instantaneously after dissociating a previously coordinated H2O.

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

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

Non-stackable molecules assemble into porous crystals displaying concerted cavity-changing motions.

With small molecules, it is not easy to create large void spaces. Flat aromatics stack tightly, while flexible chains fold to fill the cavities. As an intuitive design to make open channels inside molecularly constructed solids, we employed propeller-shaped bicyclic triazoles to prepare a series of aromatic-rich three-dimensional (3D) building blocks. This modular approach has no previous example, but is readily applicable to build linear, bent, and branched arrays of non-stackable architectural motifs from existing flat aromatics by single-pot reactions. A letter H-shaped molecule thus prepared self-assembles into porous crystals, the highly unusual stepwise gas sorption behaviour of which prompted in-depth studies. A combination of single-crystal and powder X-ray diffraction analysis revealed multiple polymorphs, and sterically allowed pathways for their reversible interconversions that open and close the pores in response to external stimuli.