Stabilization of the Low‐Spin State in a Mononuclear Iron(II) Complex and High‐Temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding

The tetrapyridyl ligand bbpya (bbpya=N,N‐bis(2,2′‐bipyrid‐6‐yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)₂] ( 1 ) were prepared. According to magnetic susceptibility, differential scanning calorimetry fitted to Sorai’s domain model, and powder X‐ray diffraction measurements, 1 is low‐spin at room temperature, and it exhibits spin crossover (SCO) at an exceptionally high transition temperature of T_1/2=418 K. Although the SCO of compound 1 spans a temperature range of more than 150 K, it is characterized by a wide (21 K) and dissymmetric hysteresis cycle, which suggests cooperativity. The crystal structure of the LS phase of compound 1 shows strong N?H???S intermolecular H‐bonding interactions that explain, at least in part, the cooperative SCO behavior observed for complex 1 . DFT and CASPT2 calculations under vacuum demonstrate that the bbpya ligand generates a stronger ligand field around the iron(II) core than its analogue bapbpy (N,N′‐di(pyrid‐2‐yl)‐2,2′‐bipyridine‐6,6′‐diamine); this stabilizes the LS state and destabilizes the HS state in 1 compared with [Fe(bapbpy)(NCS)₂] ( 2 ). Periodic DFT calculations suggest that crystal‐packing effects are significant for compound 2 , in which they destabilize the HS state by about 1500 cm^?1. The much lower transition temperature found for the SCO of 2 compared to 1 appears to be due to the combined effects of the different ligand field strengths and crystal packing.     

Non-coercive Lyapunov functions for infinite-dimensional systems

We show that the existence of a non-coercive Lyapunov function is sufficient for uniform global asymptotic stability (UGAS) of infinite-dimensional systems with external disturbances provided the speed of decay is measured in terms of the norm of the state and an additional mild assumption is satisfied. For evolution equations in Banach spaces with Lipschitz continuous nonlinearities these additional assumptions become especially simple. The results encompass some recent results on linear switched systems on Banach spaces. Finally, we derive new non-coercive converse Lyapunov theorems and give some examples showing the necessity of our assumptions.     

Synthesis,Modification, and Anticonvulsant Activity of 3′‐R1‐Spiro[indoline‐3,6′‐[1,2,4]triazino[2,3‐c]quinazolin]‐2,2′(7′H)‐diones Derivatives

Previously unknown 3′‐R¹‐5‐R²‐spiro[indoline‐3,6′‐[1,2,4]triazino[2,3‐c]quinazoline]‐2,2′‐(7′H)‐diones and their N‐substituted analogues were obtained via reaction of 6‐R¹‐3‐(2‐aminophenyl)‐1,2,4‐triazin‐5‐ones with isatin and its substituted derivatives. It was shown that alkylation of 3′‐R¹‐5‐R²‐spiro[indoline‐3,6′‐[1,2,4]triazino[2,3‐c]quinazolin]‐2,2′‐(7′H)‐diones by N‐R³‐chloroacetamides or chloroacetonitrile in the presence of а base proceeds by N‐1 atom of isatin fragment. The spectral properties (¹H and ¹³C NMR spectra) of synthesized compounds were studied, and features of spectral patterns were discussed. The high‐effective anticonvulsant and radical scavenging agents among 3′‐R¹‐5‐R²‐spiro[indoline‐3,6′‐[1,2,4]triazino[2,3‐c]quinazolin]‐2,2′(7′H)‐diones and their N‐substituted derivatives were detected. It was shown that compounds 2.2 , 2.8 , and 3.1 exceed or compete the activity of the most widely used in modern neurology drug—lamotrigine on the pentylenetetrazole‐induced seizures model. The aforementioned fact may be considered as a reason for further profound study of synthesized compounds using other pathology models.     

Oxa-spirocycles: synthesis,properties and applications

A general approach to a new generation of spirocyclic molecules – oxa-spirocycles – was developed. The key synthetic step was iodocyclization. More than 150 oxa-spirocyclic compounds were prepared. Incorporation of an oxygen atom into the spirocyclic unit dramatically improved water solubility (by up to 40 times) and lowered lipophilicity. More potent oxa-spirocyclic analogues of antihypertensive drug terazosin were synthesized and studied in vivo.

A general practical approach to a new generation of spirocyclic molecules – oxa-spirocycles – is developed.     

“Activated Borane” – A Porous Borane Cluster Network as an Effective Adsorbent for Removing Organic Pollutants

The unprecedented co-thermolysis of decaborane(14) (nido-B₁₀H₁₄) and toluene results in a novel porous material (that we have named “activated borane”) containing micropores between 1.0 and 1.5 nm in diameter and a specific surface area of 774 m² g⁻¹ (Ar, 87 K) that is thermally stable up to 1000 °C. Solid state ¹H, ¹¹B and ¹³C MAS NMR, UV-vis and IR spectroscopies suggest an amorphous structure of borane clusters interconnected by toluene moieties in a ratio of about three toluene molecules for every borane cluster. In addition, the structure contains Lewis-acidic tri-coordinated boron sites giving it some unique properties. Activated borane displays high sorption capacity for pollutants such as sulfamethoxazole, tramadol, diclofenac and bisphenol A that exceed the capacity of commercially-available activated carbon. The consistency in properties for each batch made, and the ease of its synthesis, make activated borane a promising porous material worthy of broad attention.     

N-(R-Cyclopropyl) Trifluoroacetimidoyl Phosphonates

Abstract

A convenient synthetic approach for previously unknown N-(R-cyclopropyl)trifluoroacetimidoyl phosphonates 5a,b (R?H, CF₃) was developed on the basis of the reaction of respective trifluoroacetimidoyl chlorides with triethyl phosphite. It was shown that imidoyl phosphonates 5a,b exist as equilibrium mixture of Z/E isomers (Z:E ～92:8). Activation parameters of Z–E isomerization were evaluated by ¹⁹F NMR spectroscopy. Catalytic hydrogenation of 5a,b can serve as a convenient method for the synthesis of trifluoroethylaminophosphonates with a rigid N-cyclopropyl group.     

On the role of longitudinal momenta in high energy hadron-hadron scattering

We demonstrate a new method to calculate inelastic scattering cross-sections, which in contrary to the Regge-based methods takes into account the energy momentum conservation law. It is shown that the main contribution to integral expressing inelastic scattering cross-sections does not come from the multi-Regge domain. In particular, accounting for the longitudinal momenta contribution to virtualities is sufficient and results in the new mechanism of cross-section growth. The reasons for taking into account the sufficiently high number of interference contributions are shown and the approximate method for this purpose is developed. By fitting single free parameter of the model achieved a qualitative agreement of the total and inelastic cross sections with experimental data.     

Arylidene Pyruvic Acids Motif in the Synthesis of New 2H,5H-Chromeno[4′,3′:4,5]thiopyrano[2,3-d]thiazoles via Tandem Hetero-Diels–Alder-Hemiacetal Reaction

We have developed a tandem hetero-Diels–Alder-hemiacetal reaction using arylidene pyruvic acids with 5-(ortho-hydroxybenzylidene)-substituted 4-thioxo-2-thiazolidinones, leading to 6-hydroxy-2-oxo-5-phenyl-3,5a,6,11b-tetrahydro-2H,5H-chromeno[4′,3′:4,5]thiopyrano[2,3-d][1,3]thiazole-6-carboxylic acids. The stereochemistry of cycloaddition was confirmed by NMR spectra and a single-crystal x-ray diffraction analysis.     

Metal-graphene nanostructures for SEIRA spectroscopy

Abstract

Infrared spectroscopy is widely used technique for observing bioorganic materials, but sometimes scientist have to work with small amount of investigated materials and infrared light interacts poorly with nanometric size molecules. Taking into account unique electro-optical properties of graphene and metal we demonstrated possibility to use metal-graphene nanostructures for label-free detection of thymine. It was shown that IR spectra of thymine adsorbed on the composite nanostructures, such as Au “nanostars” with graphene, is more enhanced than whenthese nanoparticles are used without graphene. The enhancement in IR absorption for complex thymine/Au/graphene depends on size of Au nanoparticlesand thymine’s molecular group.