A structural study of (1RS,2SR,3RS,4SR,5RS)‐2,4‐dibenzoyl‐1,3,5‐triphenylcyclohexan‐1‐ol chloroform hemisolvate and (1RS,2SR,3RS,4SR,5RS)‐2,4‐dibenzoyl‐1‐phenyl‐3,5‐bis(2‐methoxyphenyl)cyclohexan‐1‐ol

(1RS,2SR,3RS,4SR,5RS)‐2,4‐Dibenzoyl‐1,3,5‐triphenylcyclohexan‐1‐ol or (4‐hydroxy‐2,4,6‐triphenylcyclohexane‐1,3‐diyl)bis(phenylmethanone), C₃₈H₃₂O₃, (1), is formed as a by‐product in the NaOH‐catalyzed synthesis of 1,3,5‐triphenylpentane‐1,5‐dione from acetophenone and benzaldehyde. Single crystals of the chloroform hemisolvate, C₃₈H₃₂O₃·0.5CHCl₃, were grown from chloroform. The structure has triclinic (P) symmetry. One diastereomer [as a pair of (1RS,2SR,3RS,4SR,5RS)‐enantiomers] of (1) has been found in the crystal structure and confirmed by NMR studies. The dichoromethane hemisolvate has been reported previously [Zhang et al. (2007). Acta Cryst. E 63 , o4652]. (1RS,2SR,3RS,4SR,5RS)‐2,4‐Dibenzoyl‐3,5‐bis(2‐methoxyphenyl)‐1‐phenylcyclohexan‐1‐ol or [4‐hydroxy‐2,6‐bis(2‐methoxyphenyl)‐4‐phenylcyclohexane‐1,3‐diyl]bis(phenylmethanone), C₄₀H₃₆O₅, (2), is also formed as a by‐product, under the same conditions, from acetophenone and 2‐methoxybenzaldehyde. Crystals of (2) have been grown from chloroform. The structure has orthorhombic (Pca2₁) symmetry. A diastereomer of (2) possesses the same configuration as (1). In both structures, the cyclohexane ring adopts a chair conformation with all bulky groups (benzoyl, phenyl and 2‐methoxyphenyl) in equatorial positions. The molecules of (1) and (2) both display one intramolecular O—H...O hydrogen bond.     

Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P3N5, δ-P3N5 and PN2

Non-metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN₆ octahedra frameworks being particularly attractive. In this study, the phosphorus–nitrogen system was studied up to 137 GPa in laser-heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single-crystal X-ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ-P₃N₅ and PN₂ were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN₆ units. The two compounds are ultra-incompressible, having a bulk modulus of K₀=322 GPa for δ-P₃N₅ and 339 GPa for PN₂. Upon decompression below 7 GPa, δ-P₃N₅ undergoes a transformation into a novel α′-P₃N₅ solid, stable at ambient conditions, that has a unique structure type based on PN₄ tetrahedra. The formation of α′-P₃N₅ underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure.     

Palladium‐Catalyzed Amination of 3,5‐Dihalopyridines – a Convenient Route to New Polyazamacrocycles

Pd‐Catalyzed amination of 3,5‐dibromo‐ and 3,5‐dichloropyridine ( 1a and 1b , resp.) with linear polyamines 2 leads to the formation of a new family of pyridine‐containing macrocycles 3 with an ‘exo’‐oriented pyridine N‐atom (Schemes 1 and 2). The dependence of the macrocycle yield on the nature of the halogen atom, the length of the polyamine chain and C/N atom ratio, and the composition of the catalytic system is studied. The synthesis of mono‐ and bis(5‐halopyridin‐3‐yl)‐substituted polyamines 4, 5, 8, 9 , and of 3,5‐bis(polyamino)‐substituted pyridines 6 is described (Schemes 3 and 4), and the use of these compounds as intermediates on the way to the macrocycles 7, 16 , and 18 with larger cavity (‘cyclodimers’ and ‘cyclotrimers’) is demonstrated (Schemes 5–10).     

Erratum to: Several Articles in JETP Letters Published Online First

JETP Letters - An Erratum to this paper has been published: https://doi.org/10.1134/S0021364022330013     

High‐Pressure Synthesis of a Nitrogen‐Rich Inclusion Compound ReN8⋅x N2 with Conjugated Polymeric Nitrogen Chains

A nitrogen‐rich compound, ReN₈?x N₂, was synthesized by a direct reaction between rhenium and nitrogen at high pressure and high temperature in a laser‐heated diamond anvil cell. Single‐crystal X‐ray diffraction revealed that the crystal structure, which is based on the ReN₈ framework, has rectangular‐shaped channels that accommodate nitrogen molecules. Thus, despite a very high synthesis pressure, exceeding 100 GPa, ReN₈?x N₂ is an inclusion compound. The amount of trapped nitrogen (x) depends on the synthesis conditions. The polydiazenediyl chains [?N=N?]_∞ that constitute the framework have not been previously observed in any compound. Ab initio calculations on ReN₈?x N₂ provide strong support for the experimental results and conclusions.     

SO(4) theory of antiferromagnetism and superconductivity in Bechgaard salts

Motivated by recent experiments with Bechgaard salts, we investigate the competition between antiferromagnetism and triplet superconductivity in quasi-one-dimensional electron systems. We unify the two orders in an SO(4) symmetric framework, demonstrating the existence of such symmetry in one-dimensional Luttinger liquids. SO(4) symmetry strongly constrains the phase diagram, leading to coexistence regions of antiferromagnetic, superconducting, and normal phases, as observed in (TMTSF)(2)PF(6). We predict a sharp neutron scattering resonance in superconducting samples.     

Two new asterosaponins from the Far Eastern starfish Lethasterias fusca

Two new asterosaponins, lethasteriosides A (1) and B (2), were isolated along with previously known thornasteroside A (3), anasteroside A (4), and luidiaquinoside (5) from the ethanolic extract of the Far Eastern starfish Lethasterias fusca. The structures of the new compounds were elucidated by extensive NMR and ESIMS techniques, and chemical transformations. Compounds 1 and 3-5 did not show any apparent cytotoxicity against cancer cell lines T-47D, RPMI-7951, and HCT-116, but glycoside 1, at concentration of 20 microM, demonstrated considerable inhibition of the T-47D (97%), RPMI-795I (90%) and HCT-116 (90%) cell colony formations in a soft agar clonogenic assay.     

Granulatosides D,E and other polar steroid compounds from the starfish Choriaster granulatus. Their immunomodulatory activity and cytotoxicity

Two new steroid glycosides, granulatosides D (1) and E (2), belonging to the group of bi- and monoglycosides of polyhydroxysteroids, respectively, were isolated from the ethanolic extract of the starfish Choriaster granulatus along with thirteen previously known glycosides of polyhydroxysteroids (3–15) and one steroid heptaol (16). The structures of the new compounds were elucidated by extensive NMR and ESIMS techniques. Cytotoxic and immunomodulatory activities of compounds 1, 3–8, and 10–16 using murine splenocytes and peritoneal macrophages were studied. At a dose of 0.1 μM new glycoside 1 showed immunomodulatory properties, increasing the intracellular ROS (reactive oxygen species) level in peritoneal murine macrophages by 20% and decreasing intracellular ROS level by 21% in pre-treated with endotoxic lipopolysaccharide from E. coli (LPS) peritoneal macrophages.     

Stereospecific [2 + 2]-cross-photocycloaddition in a supramolecular donor–acceptor complex

A bis(propylammonium) derivative of (E)-4-(4-mercaptostyryl)pyridine, which was synthesized for the first time, forms a highly stable bimolecular complex with a bis(18-crown-6 ether) derivative of (E)-stilbene in solution owing to ditopic coordination via hydrogen bonds. The complex formation results in much faster deactivation of the excited states of both compounds, which is explained by photoinduced electron transfer from the stilbene derivative to the styrylpyridinium dye. Despite this, the complexed olefins undergo [2?+?2]-cross-photocycloaddition upon selective excitation of the dye to afford solely the syn-cycloadduct. The retro-photocycloaddition occurs readily upon UV irradiation of the cycloadduct and leads to the initial bimolecular complex.     

Spin-wave contribution to the nuclear spin-lattice relaxation in triplet superconductors

We discuss collective spin-wave excitations in triplet superconductors with an easy axis anisotropy for the order parameter. Using a microscopic model for interacting electrons, we estimate the frequency of such excitations in Bechgaard salts and ruthenate superconductors to be 1 and 20 GHz, respectively. We introduce an effective bosonic model to describe spin-wave excitations and calculate their contribution to the nuclear spin-lattice relaxation rate. We find that, in the experimentally relevant regime of temperatures, this mechanism leads to the power law scaling of 1/T1 with temperature. For two- and three-dimensional systems, the scaling exponents are 3 and 5, respectively. We discuss experimental manifestations of the spin-wave mechanism of the nuclear spin-lattice relaxation.