Synthesis, Raman, X-ray diffraction, and density functional studies of antimony(III) heterotetracycles displaying intramolecular transannular interactions O → Sb

A set of compounds of general formula [{S(C₆H₃S)₂O}SbHal] [Hal = Cl (1), Br (2), I (3)] has been synthesized and studied by Raman and NMR spectroscopy as well as quantum chemical DFT calculations. X-ray diffraction studies of compound 2 revealed that the oxygen atom participates as donor and the antimony atom plays the role of acceptor, adopting a Ψ-distorted trigonal bi-pyramidal geometry, where the eight-membered central ring displays a boat–boat conformation. Furthermore, a series of DFT calculations was performed on compounds 1–3 as well as calculations on the non-synthesized heterotetracyclic systems [{S(C₆H₃S)₂O}SbF] (4a) and the cation [{S(C₆H₃S)₂O}Sb]⁺ (5a). The theoretic study at DFT level indicates as the electronegativity increases at exocyclic substituent along the set of compounds, the interaction is stronger. Moreover, the topological analysis of electronic density showed the existence of critical points along the O → Sb direction which prompted us to suggest the existence of a dative bond.     

The Dielectric Tensor for Magnetized Dusty Plasmas with Superthermal Plasma Populations and Dust Particles of Different Sizes

We present general expressions for the components of the dielectric tensor of magnetized dusty plasmas, valid for arbitrary direction of propagation and for situations in which populations of dust particles of different sizes are present in the plasma. These expressions are derived using a kinetic approach which takes into account the variation of the charge of the dust particles due to inelastic collisions with electrons and ions, and features the components of the dielectric tensor in terms of a finite and an infinite series, containing all effects of harmonics and Larmor radius, and is valid for the whole range of frequencies above the plasma frequency of the dust particles, which are assumed to be motionless. The integrals in velocity space which appear in the dielectric tensor are solved assuming that the electron and ion populations are described by anisotropic non-thermal distributions characterized by parameters κ _∥ and κ _⊥, featuring the Maxwellian as a limiting case. These integrals can be written in terms of generalized dispersion functions, which can be expressed in terms of hypergeometric functions. The formulation therefore becomes specially suitable for numerical analysis.     

Symmetry breaking of optical vortices: birth and annihilation of singularities in the evanescent field

The interaction of optical vortices (or phase singularities, or screw dislocations) with ordinary matter is treated with a simple approach. Using the total internal reflection phenomenon and the superposition of four plane waves incident on a material with a refractive index lower than the original propagating medium, we are able to show the birth and annihilation of optical vortices in an evanescent field with curved topological features. Until now, this phenomenon has been explored only in free space propagation. By a suitable tuning process involving the incident angles and the amplitudes of the incident plane waves, it is possible to create unusual topological features of optical vortices in the vicinity of the material. We believe that this work can open new aspects of curved optical vortex manipulation in near-field optics.     

A 3.3 Å‐Resolution Structure of Hyperthermophilic Respiratory Complex III Reveals the Mechanism of Its Thermal Stability

Respiratory chain complexes convert energy by coupling electron flow to transmembrane proton translocation. Owing to a lack of atomic structures of cytochrome bc₁ complex (Complex III) from thermophilic bacteria, little is known about the adaptations of this macromolecular machine to hyperthermophilic environments. In this study, we purified the cytochrome bc₁ complex of Aquifex aeolicus, one of the most extreme thermophilic bacteria known, and determined its structure with and without an inhibitor at 3.3 Å resolution. Several residues unique for thermophilic bacteria were detected that provide additional stabilization for the structure. An extra transmembrane helix at the N‐terminus of cyt. c₁ was found to greatly enhance the interaction between cyt. b and cyt. c₁, and to bind a phospholipid molecule to stabilize the complex in the membrane. These results provide the structural basis for the hyperstability of the cytochrome bc₁ complex in an extreme thermal environment.     

Exploring Excited‐State Tunability in Luminescent Tris‐cyclometalated Platinum(IV) Complexes: Synthesis of Heteroleptic Derivatives and Computational Calculations

The synthesis, structure, electrochemistry, and photophysical properties of a series of heteroleptic tris‐ cyclometalated Pt^IV complexes are reported. The complexes mer‐[Pt(C^N)₂(C′^N′)]OTf, with C^N=C‐deprotonated 2‐(2,4‐difluorophenyl)pyridine (dfppy) or 2‐phenylpyridine (ppy), and C′^N′=C‐deprotonated 2‐(2‐thienyl)pyridine (thpy) or 1‐phenylisoquinoline (piq), were obtained by reacting bis‐ cyclometalated precursors [Pt(C^N)₂Cl₂] with AgOTf (2 equiv) and an excess of the N′^C′H pro‐ligand. The complex mer‐[Pt(dfppy)₂(ppy)]OTf was obtained analogously and photoisomerized to its fac counterpart. The new complexes display long‐lived luminescence at room temperature in the blue to orange color range. The emitting states involve electronic transitions almost exclusively localized on the ligand with the lowest π–π* energy gap and have very little metal character. DFT and time‐dependent DFT (TD‐DFT) calculations on mer‐[Pt(ppy)₂(C′^N′)]⁺ (C′^N′=thpy, piq) and mer/fac‐[Pt(ppy)₃]⁺ support this assignment and provide a basis for the understanding of the luminescence of tris‐cyclometalated Pt^IV complexes. Excited states of LMCT character may become thermally accessible from the emitting state in the mer isomers containing dfppy or ppy as chromophoric ligands, leading to strong nonradiative deactivation. This effect does not operate in the fac isomers or the mer complexes containing thpy or piq, for which nonradiative deactivation originates mainly from vibrational coupling to the ground state.     

Cyclic group and knapsack facets

 Any integer program may be relaxed to a group problem. We define the master cyclic group problem and several master knapsack problems, show the relationship between the problems, and give several classes of facet-defining inequalities for each problem, as well as a set of mappings that take facets from one type of master polyhedra to another. Received: May 24, 2001 / Accepted: August 2002 Published online: March 21, 2003 Mathematics Subject Classification (1991): 20E28, 20G40, 20C20     

Asymmetric induction by phase-transfer catalysis using chiral catalysts. Synthesis of 1,2-dichloroalkanes and acetylcyanohydrins

Asymmetric induction is observed in the additioin of chlorine to alkenes as well as in the synthesis of 0-acetyl cyanohydrins under phase-transfer conditions using (?)-benzylcinchonidinium chloride and (?)-N-dodecyl-N-methylephedrinium bromide as chiral catalysts.     

Temperature‐Controlled Switchable Photochromism in Solid Materials

A novel strategy to achieve thermally switchable photochromism in solid materials is reported, which relies on the preparation of polymeric core–shell capsules containing solutions of photochromic dyes in acidic phase‐change materials. Upon changing the phase (solid or liquid) of the encapsulated medium, one of the two photochromic states of the system is selectively stabilized on demand, allowing for reversible interconversion between direct and reverse photochromism when thermally scanning through the melting temperature of the phase‐change material. This strategy, which does not require the addition of external agents or chemical modification of the dyes, proved to be general for different spiropyran photochromes and to be applicable to the fabrication of a variety of functional materials by simply embedding the capsules obtained into a solid matrix of choice.