These 3p-MOFs present very high water, thermal, and chemical stability, especially for SNNU-150-Al, which can maintain its framework at 85 °C in water for 24 h and in a room-temperature environment for more than 30 days. IAST calculations, breakthrough experiments, and GCMC simulations all show that SNNU-150 MOFs have top-level C2H2/CO2 separation performance and follow the order Al-MOF > Ga-MOF > In-MOF.The production of hydrogen from ecofriendly renewable technologies like water electrolysis and fuel cells involves oxygen evolution reaction (OER), which plays a major role, but the slow kinetics of OER is a bottleneck of commercialization of such technologies. Herein, we have reported the formation of an efficient OER catalyst from SnCo(OH)6 (SCH) by leaching of Sn atoms during electrochemical OER studies. According to density functional theory calculations, adsorption of OH* species on Sn atoms is energetically more favorable than that of Co atoms, and as a result, highly active CoOOH is generated by leaching of Sn atoms from surface layers. We observed enhanced OER performance with superior mass activity by blending SCH with activated charcoal, which displays a low overpotential of 293 mV and higher mass activity than that of pristine SCH. More importantly, it outperforms Co(OH)2 and RuO2 having the same carbon composition because of the formation of thermodynamically stable and amorphous CoOOH on the surface of single-crystalline SCH and strong tethering ability of activated charcoal.Trinuclear oxothiomolybdenum(IV) glycolates (H2glyc, glycolic acid) with 2-methylimidazole (2-mim), 4-methylimidazole (4-mim), and sulfite, Na2[MoIV3(μ3-S)(μ2-O)3(glyc)3(2-mim)3]·1.5H2O (1), (4-Hmim)6[MoIV3(μ3-S)(μ2-O)3(glyc)3(4-mim)3]2[MoVIO2(glyc)2] (2), and Na3(4-Hmim)[MoIV3(μ3-S)(μ2-O)3(SO3)(glyc)3(4-mim)]·8H2O (3), have been isolated in reduced media, where 4-methylimidazole trinuclear oxothiomolybdenum(IV) glycolates in 2 coprecipitate with dioxomolybdenum(VI) glycolate, exhibiting unusual mixed valences of 4+ and 6+. Large downfield shifts of glycolates have been observed in solid-state and solution 13C (1H) NMR spectra with coordination to Mo, indicating obvious dissociation of soluble 1 and 3 in solution. Investigations of the coordination modes and conversions among the three complexes give insight into the reactivities of trinuclear oxothiomolybdenum(IV) complexes. Channels with 3.1 × 7.0 Å2 diameters exist in 2, showing reversible O2 absorption of 65.03 mg at 29.9 bar compared with little or no adsorption of N2, H2, CO2, and CH4 at room temperature, respectively. Moreover, trinuclear 2- or 4-methylimidazole oxothiomolybdenum(IV) glycolates 1 and 3 show only a few adsorptions for O2 under the same conditions.The designed synthesis of nanotwin architectures and thus-induced phase junctions expresses huge significance for semiconductor photocatalysts. However, current methods of producing nanotwins mainly involve high-temperature thermal treatment and tedious reaction steps, generally resulting in large bulk structure with ill-defined morphology and low specific surface area. Here, we propose a mild ligand-assisted coordinative self-assembly method to synthesize uniform mesoporous ZnxCd1-xS nanospheres with ultrahigh surface areas (148-312 m2 g-1) and controllable diameter (90-370 nm). Moreover, the sample possesses abundant phase junctions induced by nanotwins containing both hexagonal and cubic segments. With the synergy of the twin-induced phase junctions and high surface area, the as-prepared mesoporous Zn0.82Cd0.18S nanospheres exhibit a remarkable photocatalytic H2 evolution rate of 13.46 mmol h-1 g-1 with free noble metal. The mechanism of photocarrier dynamics was studied by transient photovoltage spectroscopy, manifesting that the photocarrier lifetime of Zn0.82Cd0.18S is largely prolonged and therefore improves the charge separation efficiency and photocatalytic activity.Fluorocarbons and chlorocarbons are common volatile organic compounds that pose serious risk to the environment and human health and therefore need to be effectively captured. Herein, we report a series of highly fluorinated metal-organic frameworks with high porosity (Brunauer-Emmett-Teller surface area ∼3000 m2/g) and stability. They show exceptionally high capacity and good recyclability toward the adsorption of fluorocarbons and chlorocarbons.In our efforts to understand the nature of metal thiolates, we have explored the chemistry of cobalt ion supported by (thiolato)phosphine ligand derivatives. Herein, we synthesized and characterized a square-planar CoII complex binding with a bidentate (thiolato)phosphine ligand, Co(PS1″)2 (1) ([PS1″]- = [P(Ph)2(C6H3-3-SiMe3-2-S)]-). The complex activates O2 to form a ligand-based oxygenation product, Co(OPS1″)2 (2) ([OPS1″]- = [PO(Ph)2(C6H3-3-SiMe3-2-S)]-). In addition, an octahedral CoIII complex with a tridentate bis(thiolato)phosphine ligand, [NEt4][Co(PS2*)2] (3) ([PS2*]2- = [P(Ph)(C6H3-3-Ph-2-S)2]2-), was obtained. Compound 3 cleaves the C-Cl bond in dichloromethane via an S-based nucleophilic attack to generate a chloromethyl thioether group. Two isomeric products, [Co(PS2*)(PSSCH2Cl*)] (4 and 4') ([PSSCH2Cl*]- = [P(Ph)(C6H3-3-Ph-2-S)(C6H3-3-Ph-2-SCH2Cl)]-), were isolated and fully characterized. Both transformations, oxygenation of a CoII-bound phosphine donor in 1 and alkylation of a CoIII-bound thiolate in 3, were monitored by spectroscopic methods. These reaction products were isolated and fully characterized.  https://www.selleckchem.com/products/bi-3802.html  Density functional theory (DFT, the B3LYP functional) calculations were performed to understand the electronic structure of 1 as well as the pathway of its transformation to 2.The reaction of PMe3 or PPh3 with PF5 in anhydrous CH2Cl2 or hexane forms the white, moisture-sensitive complexes [PF5(PR3)] (R = Me, Ph). Similar reactions involving the diphosphines o-C6H4(PR2)2 afford the complexes [PF4o-C6H4(PR2)2][PF6]. The X-ray structures of [PF5(PR3)] and [PF4o-C6H4(PMe2)2][PF6] show pseudo-octahedral fluorophosphorus centers. Multinuclear NMR spectra (1H, 19F1H, 31P1H) show that in solution in CH2Cl2/CD2Cl2 the structures determined crystallographically are the only species present for [PF5(PMe3)] and [PF4o-C6H4(PMe2)2][PF6] but that [PF5(PPh3)] and [PF4o-C6H4(PPh2)2][PF6] exhibit reversible dissociation of the phosphine at ambient temperatures, although exchange slows at low temperatures. The complex 19F1H and 31P1H NMR spectra have been analyzed, including those of the cation [PF4o-C6H4(PMe2)2]+, which is a second-order AA'XX'B2M spin system. The unstable [PF5(AsMe3)], which decomposes in a few hours at ambient temperatures, has also been isolated and spectroscopically characterized; neither AsPh3 nor SbEt3 forms similar complexes.