New synthetic protocols for the preparation of unsymmetrical bisindoles

Novel unsymmetrical bisindoles were synthesized by a solvent-free C-C bond-formation reaction under mild conditions. Starting from aziridines or hydroxyl precursors, indoles have been used as C-nucleophiles to form new pharmacologically interesting bisindoles via an electrophilic aromatic substitution pathway in good to excellent yields. [reaction: see text]     

Ultrafast transverse thermoelectric response in c‐axis inclined epitaxial La0.5Sr0.5CoO3 thin films

Ultrafast transverse thermoelectric voltage response has been observed in c‐axis inclined epitaxial La_0.5Sr_0.5CoO₃thin films. Voltage signals with the rise time of 7 ns have been detected under the irradiation of pulse laser with duration of 28 ns. A concept, named response rate ratio, has been proposed to evaluate the intrinsic response rate, and this ratio in La_0.5Sr_0.5CoO₃is smaller than that in other reported materials. The low resistivity is thought to be responsible for the ultrafast response, as low resistivity induces small optical penetration depth, and response time has a monotonous increasing relationship with this depth.

     

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.     

Experimental and Theoretical Investigations of Structural Isomers of Dichalcogenoimidodiphosphinate Dimers: Dichalcogenides or Spirocyclic Contact Ion Pairs?

A synthetic protocol for the tert-butyl-substituted dichalcogenoimidodiphosphinates [Na(tmeda){(EPtBu(2))(2)N}] (3 a, E=S; 3 b, E=Se; 3 c, E=Te) has been developed. The one-electron oxidation of the sodium complexes [Na(tmeda){(EPR(2))(2)N}] with iodine produces a series of neutral dimers (EPR(2)NPR(2)E--)(2) (4 b, E=Se, R=iPr; 4 c, E=Te, R=iPr; 5 a, E=S, R=tBu; 5 b, E=Se, R=tBu; 5 c, E=Te, R=tBu). Attempts to prepare 4 a (E=S, R=iPr) in a similar manner produced a mixture including HN(SPiPr(2)). Compounds 4 b, 4 c and 5 a-c were characterised by multinuclear NMR spectra and by X-ray crystallography, which revealed two alternative structures for these dimeric molecules. The derivatives 4 b, 4 c, 5 a and 5 b exhibit acyclic structures with a central chalcogen-chalcogen linkage that is elongated by approximately 2 % (E=S), 6 % (E=Se) and 8 % (E=Te) compared to typical single-bond values. By contrast, 5 c adopts an unique spirocyclic contact ion-pair structure in which a [(TePtBu(2))(2)N](-) ion is Te,Te' chelated to an incipient [(TePtBu(2))(2)N](+) cyclic ion. DFT calculations of the relative energies of the two structural isomers indicate a trend towards increasing stability for the contact ion pair relative to the corresponding dichalcogenide on going from S to Se to Te for both the isopropyl and tert-butyl series. The two-electron oxidation of [Na(tmeda){(EPtBu(2))(2)N}] (E=S, Se, Te) with iodine produced the salts [(EPtBu(2))(2)N](+)X(-) (7 a, E=S, X=I(3); 7 b, E=Se, X=I; 7 c, E=Te, X=I), which were characterised by X-ray crystallography. Compound 7 a exists as a monomeric, ion-separated complex with [d(S--S)=2.084(2) A]; 7 b and 7 c are dimeric [d(Se--Se)=2.502(1) A; d(Te--Te)=2.884(1) A].     

Absolute Rate Constants for the Addition of the 2‐(Methoxycarbonyl)propan‐2‐yl and the 3,3,3‐Trifluoracetonyl Radicals to Alkenes in Solution

Absolute rate constants and some of their Arrhenius parameters were obtained by time‐resolved electron spin resonance (ESR) spectroscopy for the addition of the 2‐(alkoxycarbonyl)propan‐2‐yl and 3,3,3‐trifluoroacetonyl (=3,3,3‐trifluoro‐2‐oxopropyl) radicals to a variety of mono‐ and 1,1‐disubstituted alkenes. Their analysis shows that the addition of 2‐(alkoxycarbonyl)propan‐2‐yl is mainly governed by the exothermicity of the reaction with slight modifications by nucleophilic and electrophilic effects giving rise to an overall ambiphilic behavior. In contrast, large electrophilic polar effects dominate the addition of the 3,3,3‐trifluoroacetonyl (=3,3,3‐trifluoro‐2‐oxopropan‐2‐yl) radical, as it is expected from its large electron affinity. For both radicals, the activation energies are well‐predicted by analytic equations for the enthalpic and polar terms. A comparison of the rate data of 2‐(alkoxycarbonyl)propan‐2‐yl with the homo‐ and copolymerization rate constants of the propagating radical of methyl methacrylate shows that the additions of these structurally related low‐ and high‐molecular‐weight radicals to alkenes are governed by very similar effects.     

Structure and dynamics of tetrakis(thiophosphinato)resorcinarene complexes of silver(I), gold(I), and palladium(II)

The coordination chemistry of the tetrakis(thiophosphinato)resorcinarene sulfur-donor ligands [(C6H2CH{CH2CH2Ph})4{OC(O)R}4{OP(=S)Ph2}4] (L), where R = OCH2Ph, 4-C6H4CH3, C6H11, C4H3S, or OCH2CCH, is reported. Both silver(I) and gold(I) form cationic complexes of the type [LM2]2+, in which the ligand acts as a bis(chelate) in forming complexes with linear S-M-S (M = Ag or Au) stereochemistry. Gold(I) also forms the unusual complex [L(AuCl)2][LAu2]2+, which forms a supramolecular polymer through intermolecular aurophilic attractions. Palladium(II) forms the complex [LPd2Cl2(mu-Cl)2], in which the dipalladium(II) unit extends the natural bowl structure of the resorcinarene. The solid-state and solution conformations of the complexes, as determined by X-ray structure determination and NMR spectroscopy, respectively, are similar, but several complexes were found to exhibit dynamic behavior in solution, involving either conformational mobility of the resorcinarene unit or intermolecular ligand exchange.     

Testing the Universality of Free Fall for Charged Particles in Space

At first a short analysis of the notion of the Universality of Free Fall (UFF) for charged matter is given. Even if neutral bound systems of charged particles are in full accordance with the UFF, there is still a possibility that an isolated charge couples anomalously to gravitational fields. The experiment of Witteborn and Fairbank aimed at testing the UFF for electrons is shortly reviewed emphasizing the various additional disturbing gravity induced electromagnetic fields. Since these additional gravity induced fields are not very well under control, a space borne version of this experiment will reduce these disturbances considerably. The corresponding estimates for these kinds of tests in space are presented. As a result, gravity–induced stray field can be reduced considerably. Furthermore, also patch–effects can be reduced efficiently due to novel coating techniques. Therefore, due to microgravity conditions and new techniques the UFF for charged particles may be tested with much higher accuracy than in previous experiments.