Surface modified copper foam with cobalt phthalocyanine carbon nanotube hybrids for tuning CO2 reduction reaction products.

The CO2 reduction reaction (CO2RR) is a feasible way to convert this greenhouse gas into molecules of industrial interest. Herein we present the modification of the Cu foam cathode using molecular catalyst hybrid from cobalt phthalocyanine (CoPc) to increase selectivity and stability towards CO2RR products in a flow cell setup.

Palladium Phthalocyanine Nanowire-Based Highly Sensitive Sensors for NO2(g) Detection.

Palladium phthalocyanine (PdPc) nanowires (NWs) were developed to achieve the gas sensing of NO2 in the sub-parts-per-million (ppm) range. Non-substituted metal phthalocyanine are well known for their p-type semiconducting behavior, which is responsible for its gas-sensing capabilities. Nanofabrication of the PdPc NWs was performed by physical vapor deposition (PVD) on an interdigitated gold electrode (IDE). The coordination of palladium in the structure was confirmed with UV-Vis spectroscopy. Gas-sensing experiments for NO2 detection were undertaken at different sensed gas concentrations from 4 ppm to 0.5 ppm at room temperature. In this work, the responses at different gas concentrations are reported. In addition, structural studies of the PdPc NWs with scanning electron microscopy (SEM) and electron-dispersive X-ray diffraction (EDS) are shown.

New copper carboxyl-ate pyrene dimers: synthesis, crystal structure, Hirshfeld surface analysis and electrochemical characterization.

Two new copper dimers, namely, bis-(dimethyl sulfoxide)-tetra-kis-(µ-pyrene-1-carboxyl-ato)dicopper(Cu-Cu), [Cu2(C17H9O2)4(C2H6OS)2] or [Cu2(pyr-COO-)4(DMSO)2] (1), and bis-(di-methyl-formamide)-tetra-kis-(µ-pyrene-1-carboxyl-ato)dicopper(Cu-Cu), [Cu2(C17H9O2)4(C3H7NO)2] or [Cu2(pyr-COO-)4(DMF)2] (2) (pyr = pyrene), were synthesized from the reaction of pyrene-1-carb-oxy-lic acid, copper(II) nitrate and tri-ethyl-amine from solvents DMSO and DMF, respectively. While 1 crystallized in the space group P , the crystal structure of 2 is in space group P21/n. The Cu atoms have octa-hedral geometries, with four oxygen atoms from carboxyl-ate pyrene ligands occupying the equatorial positions, a solvent mol-ecule coordinating at one of the axial positions, and a Cu⋯Cu contact in the opposite position. The packing in the crystal structures exhibits π-π stacking inter-actions and short contacts through the solvent mol-ecules. The Hirshfeld surfaces and two-dimensional fingerprint plots were generated for both compounds to better understand the inter-molecular inter-actions and the contribution of heteroatoms from the solvent ligands to the crystal packing. In addition, a Cu2+/Cu1+ quasi-reversible redox process was identified for compound 2 using cyclic voltammetry that accounts for a diffusion-controlled electron-donation process to the Cu dimer.

Crystal structure, Hirshfeld surface analysis and spectroscopic characterization of the di-enol tautomeric form of the compound 3,3'-[(2-sulf-an-yl-idene-1,3-di-thiole-4,5-di-yl)bis-(sulfane-di-yl)]bis-(pentane-2,4-dione).

The reaction between [TBA]2[Zn(dmit)2] and 3-chloro-2,4-penta-nedione yielded single crystals of the title compound, (3E,3'E)-3,3'-[(2-sulfanylidene-1,3-dithiole-4,5-diyl)bis(sulfanediyl)]bis(4-hydroxypent-3-en-2-one), C13H14O4S5, after solvent evaporation. The title compound crystallizes in the triclinic space group P with two mol-ecules related by an inversion center present in the unit cell. The central thione ring moiety contains a carbon-carbon double bond covalently linked to two sulfoxide substituents located outside of the plane of the ring. The S-C-C-S torsion angles are -176.18 (8) and -0.54 (18)°. Intra-molecular hydrogen bonds occur within the two dione substituents (1.67-1.69 Å). Adjacent asymmetric units are linked by C-H⋯S (2.89-2.90 Å), S⋯S [3.569 (1) Å] and O⋯H [2.56-2.66 Šbetween non-stacked thione rings] short contacts.

Crystal structure of 1-ferrocenyl-2-(4-nitro-phen-yl)ethyne.

The title ferrocene derivative, [Fe(C5H5)2(C8NO2)], including an alkyne bonded to a para-nitro-phenyl substituent, which was synthesized from a copper-free Sonogashira cross-coupling reaction between ethynylferrocene and 4-bromo-1-nitro-benzene, crystallizes in the P21/n space group. In the ferrocene unit, the penta-dienyl (Cps) rings are in an eclipsed conformation. The angle of rotation between the substituted cyclo-penta-dienyl ring and the p-nitro-phenyl group is 6.19 (10)°, yielding a quasi-linear extension of the ferrocenyl substitution. Important inter-molecular inter-actions arise from π-π stacking between the Cp rings and the p-nitro-phenyl, from corners of the Cp rings that are perpendicularly aligned, and between the O atoms from the nitro substituent and carbons at the corners of the Cp rings, propagating along all three crystallographic axes.

Crystal structure of a nickel compound comprising two nickel(II) complexes with different ligand environments: [Ni(tren)(H2O)2][Ni(H2O)6](SO4)2.

The title compound, di-aqua-[tris-(2-amino-eth-yl)amine]-nickel(II) hexa-aqua-nickel(II) bis-(sulfate), [Ni(C6H18N4)(H2O)2][Ni(H2O)6](SO4)2 or [Ni(tren)(H2O)2][Ni(H2O)6](SO4)2, consists of two octa-hedral nickel complexes within the same unit cell. These metal complexes are formed from the reaction of [Ni(H2O)6](SO4) and the ligand tris-(2-amino-eth-yl)amine (tren). The crystals of the title compound are purple, different from those of the starting complex [Ni(H2O)6](SO4), which are turquoise. The reaction was performed both in a 1:1 and 1:2 metal-ligand molar ratio, always yielding the co-precipitation of the two types of crystals. The asymmetric unit of the title compound, which crystallizes in the space group Pnma, consists of two half NiII complexes and a sulfate counter-anion. The mononuclear cationic complex [Ni(tren)(H2O)2]2+ comprises an Ni ion, the tren ligand and two water mol-ecules, while the mononuclear complex [Ni(H2O)6]2+ consists of another Ni ion surrounded by six coordinated water mol-ecules. The [Ni(tren)(H2O)2] and [Ni(H2O)6] subunits are connected to the SO4 2- counter-anions through hydrogen bonding, thus consolidating the crystal structure.

Structural characterization and Hirshfeld surface analysis of 2-iodo-4-(penta-fluoro-λ6-sulfan-yl)benzo-nitrile.

The title compound, C7H3F5INS, a penta-fluoro-sulfanyl (SF5) containing arene, was synthesized from 4-(penta-fluoro-sulfan-yl)benzo-nitrile and lithium tetra-methyl-piperidide following a variation to the standard approach, which features simple and mild conditions that allow direct access to tri-substituted SF5 inter-mediates that have not been demonstrated using previous methods. The mol-ecule displays a planar geometry with the benzene ring in the same plane as its three substituents. It lies on a mirror plane perpendicular to [010] with the iodo, cyano, and the sulfur and axial fluorine atoms of the penta-fluoro-sulfanyl substituent in the plane of the mol-ecule. The equatorial F atoms have symmetry-related counterparts generated by the mirror plane. The penta-fluoro-sulfanyl group exhibits a staggered fashion relative to the ring and the two hydrogen atoms ortho to the substituent. S-F bond lengths of the penta-fluoro-sulfanyl group are unequal: the equatorial bond facing the iodo moiety has a longer distance [1.572 (3) Å] and wider angle compared to that facing the side of the mol-ecules with two hydrogen atoms [1.561 (4) Å]. As expected, the axial S-F bond is the longest [1.582 (5) Å]. In the crystal, in-plane C-H⋯F and N⋯I inter-actions as well as out-of-plane F⋯C inter-actions are observed. According to the Hirshfeld analysis, the principal inter-molecular contacts for the title compound are F⋯H (29.4%), F⋯I (15.8%), F⋯N (11.4%), F⋯F (6.0%), N⋯I (5.6%) and F⋯C (4.5%).

Simalikalactone D, a Potential Anticancer Compound from Simarouba tulae, an Endemic Plant of Puerto Rico.

Species of the genus Simarouba have been studied because of their antimalarial and antileukemic activities. A group of oxygenated terpenes called quassinoids have been isolated from species of the Simarouba genus, and are responsible for its therapeutic properties. We hypothesized that Simarouba tulae, an endemic plant from Puerto Rico, is a natural source rich in quassinoid compounds with anticancer activity. The leaves were processed and extracted with solvents of different polarities. The extracts were screened for their antiproliferative activity, and it was shown that the chloroform extract was the most active extract. This extract was purified using different chromatographic techniques to afford the quassinoid simalikalactone D (SKD). This compound was further characterized using NMR and X-ray diffraction analysis. A reassessment of original structural assignments for SKD is proposed. SKD showed high cytotoxicity activity, with an IC50 of 55, 58, and 65 nM in A2780CP20 (ovarian), MDA-MB-435 (breast), and MDA-MB-231 (breast) cell lines, respectively. Exposure to SKD led to 15% inhibition of the migration of MDA-MB-231 cells.

Crystal structure of (-)-(S)-4-[(2S,3S,4S,Z)-3-hydroxy-4-methyl-hept-5-en-2-yl]-1,3-dioxolan-2-one.

The title compound, C11H18O4, consists of an anti,anti,anti-stereo-tetrad with a 1,2-carbonate and an alkene motif. The mol-ecule displays a common zigzag conformation. The five-membered ring has a twisted conformation on the C-C bond. In the crystal, a strong inter-molecular hydrogen bond between the hy-droxy group and the carboxyl-ate moiety from an adjacent mol-ecule forms chains propagating along the b-axis direction. The absolute structure of the mol-ecule in the crystal was determined by resonant scattering [Flack parameter = 0.05 (6)].

Crystal structure of (-)-(2R,3S,4R,5R)-5-(1,3-di-thian-2-yl)-3-methyl-1-(triiso-propyl-sil-yloxy)hexane-2,4-diol.

The title compound, C20H42O3S2Si, crystallized with two independent mol-ecules (A and B) in the asymmetric unit. They consist of syn,anti,anti-stereo-tetrads with a 1,3-di-thiane motif and a primary alcohol protected as the triisopropyl silyl ether. The 1,3-di-thiane ring adopts a chair conformation, while the rest of each mol-ecule displays a common zigzag conformation. There is an intra-molecular O-H⋯O hydrogen bond in each mol-ecule. In the crystal, the A and B mol-ecules are linked via O-H⋯O hydrogen bonds, forming -A-B-A--B-- chains along [010]. The absolute structure was determined by resonant scattering (anomalous scattering) [Flack parameter = 0.035 (8)].