Bidentate Phosphanyl- and Arsanylboranes

A new class of neutral bidentate ligands with pnictogenyl-functional sites has been obtained. The reaction of tmeda⋅(BH₂I)₂ ( 1 , tmeda=tetramethylethylendiamine) with different phosphanides yields the corresponding bidentate phosphanylboranes tmeda⋅(BH₂PH₂)₂ ( 2 a ), tmeda⋅(BH₂PPh₂)₂ ( 2 b ), and tmeda⋅(BH₂tBuPH)₂ ( 2 c ). This reaction strategy could be further extended to synthesize the first bidentate arsanylborane tmeda⋅(BH₂AsPh₂)₂ ( 3 ). Depending on the substituents on the phosphorus, these compounds form different Au^I complexes, to build either polymeric tmeda⋅(BH₂PH₂AuCl)₂ ( 4 a ), or monomeric tmeda⋅(BH₂PPh₂AuCl)₂ ( 4 b ) products. These compounds form also neutral oligomeric group 13/15 chain-like molecules by coordination to a boron moiety such as tmeda⋅(BH₂PH₂BH₃)₂ ( 5 a ) and tmeda⋅(BH₂AsPh₂BH₃)₂ ( 5 b ). DFT calculations provide insight into the differences between the syntheses of mono- and bidentate pnictogenylboranes.     

Solid-State NMR Spectroscopy: A Powerful Technique to Directly Study Small Gas Molecules Adsorbed in Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have shown great potential in gas separation and storage, and the design of MOFs for these purposes is an on-going field of research. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a valuable technique for characterizing these functional materials. It can provide a wide range of structural and motional insights that are complementary to and/or difficult to access with alternative methods. In this Concept article, the recent advances made in SSNMR investigations of small gas molecules (i.e., carbon dioxide, carbon monoxide, hydrogen gas and light hydrocarbons) adsorbed in MOFs are discussed. These studies demonstrate the breadth of information that can be obtained by SSNMR spectroscopy, such as the number and location of guest adsorption sites, host–guest binding strengths and guest mobility. The knowledge acquired from these experiments yields a powerful tool for progress in MOF development.     

Synthesis,Crystal Structure,and Selected Properties of [Au(S2CNH2)2]SCN: A Precursor for Gold Macro-Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride

A new preparation route is developed for the synthesis of needle-like crystals of [Au(S₂CNH₂)₂]SCN, which avoids disproportionation of the Au^I salt used as a starting material. In the crystal structure, the two crystallographically independent Au^III centers are in a square-planar environment of two S₂CNH₂ ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 μm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)₂N. ¹³C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles.     

Cover Feature: How Many O-Donor Groups in Enterobactin Does It Take to Bind a Metal Cation? (Chem. Eur. J. 28/2019)

The E. coli siderophore enterobactin, the strongest Fe^III chelator known to date, forms hexacoordinate complexes with Si^IV, Ge^IV, and Ti^IV. Synthetic protocols have been developed to prepare non-symmetric enterobactin analogues with varying denticities. Various benzoic acid residues were coupled to the macrocyclic lactone to afford a diverse library of ligands. These enterobactin analogues were bound to Si^IV, Ge^IV, and Ti^IV, and the complexes were investigated through experimental and computational techniques. The binding behavior of the synthesized chelators enabled assessment of the contribution of each of the phenolic hydroxy groups in enterobactin to metal-ion complexation. It was found that at least four O-donors are needed for enterobactin derivatives to act as metal binders. Density functional theory calculations indicate that the strong binding behavior of enterobactin can be ascribed to a diminished translational entropy penalty, a common feature of the chelate effect, coupled with the structural arrangement of the three catechol moieties, which allows the triseryl base to be installed without distorting the preferred local metal-binding geometry of the catecholate ligands.     

Crystal structure and computational studies of (E)-1-(benzo[b]thiophen-3-yl)-N-(4-ethoxyphenyl)methanimine

Crystallography Reports - The title compound, C17H15NOS, crystallizes in the orthorhombic sp. gr. Pca21. Two molecules in the asymmetric unit have similar structure. Crystal structure contains weak...     

Novel parameter estimation techniques for a multi-term fractional dynamical epidemic model of dengue fever

Numerical Algorithms - An inverse problem to identify parameters for the single-term (and multi-term) fractional-order system of an outbreak of dengue fever is considered. Firstly, we propose a...     

Statistics and characterization of matrices by determinant and trace

The Ramanujan Journal - Answering a question of Erdös, Komlós proved in 1968 that almost all $$n\times n$$ Bernoulli matrices are nonsingular as $$n\rightarrow \infty $$ . In this paper,...     

On the difference spaces of almost convergent and strongly almost convergent double sequences

In this paper, we study the difference spaces \({\mathcal {F}}(\varDelta )\), \({\mathcal {F}}_0(\varDelta )\), \({\mathcal {[F]}}(\varDelta )\) and \({\mathcal {[F]}}_0(\varDelta )\) of double sequences obtained as the domain of four-dimensional backward difference matrix \(\varDelta \) in the spaces \({\mathcal {F}}\), \({\mathcal {F}}_{0}\), \({\mathcal {[F]}}\) and \({\mathcal {[F]}}_{0}\) of almost convergent, almost null, strongly almost convergent and strongly almost null double sequences; respectively. We examine general topological properties of those spaces and give some inclusion theorems. Furthermore, we deal with their dual spaces.