Inorganic Chemistry

The unusually high oxidation state + IV of cobalt is stabilized by ligands based on [B11 H11 ]4- in dark blue colored Cs4 [Co(B11 H10.11 (OH)0.75 )2 ]·4.56H2 O, K4 [Co(B11 H9.19 (OH)1.81 )2 ]·2H2 O, Cs8 [Co{(B11 H6 )2 (O)(O2 BOH)4 }]2 ·4H2 O and K4 [Co{(B11 H6 )2 (O2 BOH)5 }]·7H2 O. These compounds were obtained by reacting Co2+ salts with [B11 H14 ]- under alkaline conditions. In the absence of oxygen, Co(+III) compounds such as the light brownish K4 [Co(B11 H11 )(CN)3 ]·KCl·2...

[Pt(NCN)MeCN]+ (NCN = 1,3-di(2-pyridyl)benzene, MeCN = acetonitrile) forms oligomers, such as dimers and trimers, in solutions due to metallophilic interactions. The emission and absorption spectra in the visible region are considerably changed by the concentrations of the solutions because the excitation energy of the oligomers is dependent on the degree of oligomerization. In this study, excited-state dynamics of [Pt(NCN)MeCN]+ in acetonitrile were investigated by time-resolved emission spectroscopy in time regions from microseconds to nanoseconds at various concentrations...

The significant threat posed by the high toxicity of heavy metals and antibiotics in water pollutants has prompted a growing emphasis on the development of highly efficient removal methods for these pollutants. In this paper, flexible electrospinning polyacrylonitrile (PAN) nanofiber-supported CdBi2 S4 was synthesized via a hydrothermal method, followed by amination treatment with diethylenetriamine (DETA). The as-prepared CdBi2 S4 /NH2 -PAN nanofiber, enriched with sulfur vacancies, demonstrated outstanding visible-light trapping ability and a suitable band gap, leading to efficient separation and transport of photogenerated carriers, ultimately resulting in exceptional photocatalytic capability...

In the present study, we have investigated the stability of different Ba-Si clathrates with pressure and temperature using DFT calculations and studied the stability of type I Ba8 Si46 and type IX Ba24 Si100 clathrates using high pressure─high temperature synthesis technique, calorimetry, and diffraction experiments. When increasing pressure, the type I Ba8 Si46 clathrate and BaSi6 become more stable. In good qualitative agreement with experiments, the type IX Ba24 Si100 clathrate becomes stable at a pressure of 1-2 GPa thanks to the pressure and thermal effect of both electronic and vibrational contributions...

Transparent and brown La2 O3 -MoO3 binary glasses were prepared in bulk form using a levitation technique. The glass-forming range was limited, with the primary composition being approximately 25 mol % La2 O3 . The 25La2 O3 -75MoO3 glass exhibited a clear crystallization at 546 °C, while determining its glass transition temperature was difficult. Notably, despite its amorphous nature, the glass possessed a density and packing density comparable to those of crystalline La2 Mo3 O12 . X-ray absorption fine structure and Raman scattering analyses revealed that the glass structure closely resembles La2 Mo3 O12 due to the presence of isolated MoO4 2- units, whereas disordered atomic arrangement around La atoms was confirmed...

Introduction of oxygen into aromatic C-H bonds is intriguing from both fundamental and practical perspectives. Although the 3d metal-catalyzed hydroxylation of arenes by H2 O2 has been developed by several prominent researchers, a definitive mechanism for these crucial transformations remains elusive. Herein, density functional theory calculations were used to shed light on the mechanism of the established hydroxylation reaction of benzene with H2 O2 , catalyzed by [NiII (tepa)]2+ (tepa = tris[2-(pyridin-2-yl)ethyl]amine)...

Recently emerging perovskite nanocrystals (PNCs) are very attractive fluorescence nanomaterials due to their very narrow emission peak, tunable wavelength, and extremely high quantum yield, but their chemosensing, biosensing and bioimaging applications suffer from the poor stability of ordinary PNCs in aqueous media, especially in biological matrices. Recently developed water-stable 2D CsPb2 Br5 -encapsulated 3D CsPbBr3 PNCs (i.e., CsPbBr3 /CsPb2 Br5 PNCs) show extremely stable light emission in pure water, but their fluorescence is seriously quenched in aqueous media containing biological molecules due to their chemical reactions...

The reactions of two highly strained cyclopropenimine ligands L1H and L2H ( L1H = N 1 ,N 1 ,N 2 ,N 2 -tetraisopropyl-3-iminocycloprop-1-ene-1,2-diamine, L2H = N 1 ,N 1 ,N 2 ,N 2 -tetracyclohexyl-3-iminocycloprop-1-ene-1,2-diamine) with three thorium precursors Cp*2 ThCl2 , Cp*2 Th(Cl)(CH3 ), and Cp*2 Th(CH3 )2 were studied. At -20 °C, L1H and L2H react with Cp*2 ThCl2 to form Th1 ( Th1 = Cp*2 ThCl2 (L1H)) and Th2 ( Th2 = Cp*2 ThCl2 (L2H)), respectively, where the neutral ligand coordinates to the thorium metal center...

An extremely bulky p -terphenyl bis(aniline), p -C6 H4 {C6 H4 [N(H)TCHP]-2}2 (TCHP = 2,4,6-tricyclohexylphenyl) TCHP TerphH2 , has been developed. Deprotonation of a less bulky analogue, Dip TerphH2 (Dip = 2,6-diisopropylphenyl), with BePh2 affords the bimetallic system, [(BePh)2 (μ-Dip Terph)] 1 . Treating either TCHP TerphH2 or Dip TerphH2 with Mg{CH2 (SiMe3 )}2 gives the monomeric bis(anilide) complexes [Mg(Ar Terph)] (Ar = Dip 2 , TCHP 3 ) which display rare examples of η6 -arene coordination to the metal center...

Metal-mediated self-assembly of isocyanides and methyl 4-aminopyrimidine-5-carboxylate leads to luminescent PdII and PtII complexes featuring C,N-cyclometalated acyclic diaminocarbene (ADC) ligands. The solid-state luminescent properties of these diaminocarbene derivatives are attributed to their triplet-state metal/metal-to-ligand charge-transfer (3 MMLCT) nature, which is driven by attractive intermolecular M···M interactions further reinforced by the intramolecular π-π interactions even in the structure of the Pd compound, which is the first Pd-ADC phosphor reported...

Most 3d metal-based single-molecule magnets (SMMs) use N-ligands or ligands with even softer donors to impart a particular coordination geometry and increase the zero-field splitting parameter | D |, while complexes with hard O-donor ligands showing slow magnetization relaxation are rare. Here, we report that a diamagnetic NiII complex of a tetradentate ligand featuring two N -heterocyclic carbene and two alkoxide-O donors, [LO,O Ni], can serve as a {O,O'}-chelating metalloligand to give a trinuclear complex [(LO,O Ni)Co(LO,O Ni)](OTf)2 ( 2 ) with an elongated tetrahedral {CoII O4 } core, D = -74...

Nickel-rich layered oxides are envisaged as one of the most promising alternative cathode materials for lithium-ion batteries, considering their capabilities to achieve ultrahigh energy density at an affordable cost. Nonetheless, with increasing Ni content in the cathodes comes a severe extent of Ni4+ redox side reactions on the interface, leading to fast capacity decay and structural stability fading over extended cycles. Herein, dual additives of bis(vinylsulfonyl)methane (BVM) and lithium difluorophosphate (LiDFP) are adopted to synergistically generate the F-, P-, and S-rich passivation layer on the cathode, and the Ni4+ activity and dissolution at high voltage are restricted...

Dinuclear ruthenium paddlewheel complexes exhibit high structural stability in redox reactions. The use of these chemical motifs for the construction of Ru-based metal-organic polyhedra (RuMOPs) provides a route for redox-active porous materials. However, there are few studies on the synthesis and characterization of RuMOPs due to the difficulty in controlling the assembly process via the ligand-exchange reaction of equatorial acetates of the diruthenium tetraacetate precursors with dicarboxylic acid ligands...

Two-dimensional (2D) hybrid organic-inorganic perovskites constitute a versatile class of materials applied to a variety of optoelectronic devices. These materials are composed of alternating layers of inorganic lead halide octahedra and organic ammonium cations. Most perovskite research studies so far have focused on organic sublattices based on phenethylammonium and alkylammonium cations, which are packed by van der Waals cohesive forces. Here, we report a more complex organic sublattice containing benzotriazole-based ammonium cations packed through interdigitated π-π stacking and hydrogen bonding...

Colloidal II-VI semiconductor nanoplatelets (NPLs) provide a new platform in material science due to their unique growth mode and advanced optical properties. However, in contrast to the rapid development of zinc blend structured NPLs, studies on the formation of wurtzite (WZ) NPLs have been limited to the lamellar assembly of specific magic-sized nanoclusters (MSCs). Therefore, the study of new precursors is important for enriching the synthesis strategy, improving the study of two-dimensional (2D) nanocrystal growth mechanisms, and constructing complex nanostructures...

Urea oxidation reaction (UOR) is one of the potential routes in which urea-rich wastewater is used as a source of energy for hydrogen production. Metal-organic frameworks (MOFs) have promising applications in electrocatalytic processes, although there are still challenges in identifying the MOFs' molecular regulation and obtaining practical catalytic systems. The current study sought to synthesize [Zn6 (IDC)4 (OH)2 (Hprz)2 ] n (Zn-MOF) with three symmetrically independent Zn(II) cations connected via linear N-donor piperazine (Hprz), rigid planar imidazole-4,5-dicarboxylate (IDC3- ), and -OH ligands, revealing the 3,4T1 topology...

A unique assembly of a two-electron superatom, [Ag10 {S2 P(O i Pr)2 }8 ], as a primary building unit in the construction of a supramolecule [Ag10 {S2 P(O i Pr)2 }8 ]2 (μ-4,4'-bpy) through a 4,4'-bipyridine (4,4'-bpy) linker is reported. This approach is facilitated by an open site in the structure that allows for effective pairing. The assembled structure demonstrates a minimal solvatochromic shift across organic solvents with variable polarities, highlighting the influence of self-assembly on the photophysical properties of silver nanoclusters...

Organometallic-polyoxometalate (POM) complexes form a unique class of molecular organometallic oxides characterized by the dynamic behavior of the organometallic cations. Herein, we investigated the reactivity of Cp*Ir-octatungstate clusters (where Cp* represents pentamethylcyclopentadienyl, C5 Me5 - ) with Werner-type transition-metal aquo cations. The addition of Ag+ , Co2+ , Ni2+ , and M3+ (M = Cr, Fe, or In) cations to the aqueous solution of Cp*Ir-octatungstate clusters resulted in the formation of [{Ag(OH2 )2 }2 {Cp*Ir(OH2 )}2 {Cp*IrW3 O12 (OH)}2 (WO2 )2 ] ( 1 ), Co1...

One-dimensional nanostructures, with a high ratio of surface-bulk atoms, find applications as active catalysts. Here, we report tunability in ultrathin single-crystalline AuPdPt nanowires by modifying synthesis conditions and postsynthetic treatment in a controlled ambient atmosphere. The surface microstructure modification of these nanostructures has been analyzed by integrating the results of three crucial techniques including Z-contrast HAADF-STEM imaging, X-ray photoelectron spectroscopy, and electrochemically active surface area from cyclic voltammograms...

Assembling a heterostructure is an effective strategy for enhancing the electrocatalytic activity of hybrid materials. Herein, CoFe-layered double hydroxide and Co-metal-organic framework (CoFe-LDH/Co-MOF) hollow heterostructure nanorod arrays are synthesized. First, [Co(DIPL)(H3 BTC)(H2 O)2 ] n [named as Co-MOF, DIPL = 2,6-di(pyrid-4-yl)-4-phenylpyridine, H3 BTC = 1,3,5-benzenetricarboxylic acid] crystalline materials with a uniform hollow structure were prepared on the nickel foam. The CoFe-LDH/Co-MOF composite perfectly inherits the original hollow nanorod array morphology after the subsequent electrodeposition process...