(L)2C2P2: Dicarbondiphosphide Stabilized by N-Heterocyclic Carbenes or Cyclic Diamido Carbenes

Carbon phosphides, C_nP_m, may have highly promising electronic, optical, and mechanical properties, but they are experimentally almost unexplored materials. Phosphaheteroallenes stabilized by N-heterocyclic carbenes undergo a one-electron reduction to yield compounds of the type (L)₂C₂P₂ with diverse structures. The use of imidazolylidenes as ligands L give complexes with a central four-membered ring C₂P₂, while more electrophilic cyclic diamidocarbenes (DAC) give a compound with an acyclic π-conjugated CP−PC unit. Cyclic C₂P₂ compounds are best described as non-Kekulé molecules that are stabilized by coordination to the NHC ligands NHC→(C₂P₂)←NHC. These species can be easily oxidized to give stable radical cations [(NHC)₂C₂P₂]^+.. The remarkably stable molecules with an acylic C₂P₂ core are best described with electron-sharing bonds (DAC)=C=P−P=C=(DAC).     

Monitoring morphological and optical properties on hybrid porous polymer films

This work focuses on an optical and morphological comparative study of hybrid functional polymer porous films on glass substrates using the spin coating technique. The covering of these membranes, by a predeposited Zn²⁺ seed layer, was done applying the dip casting technique, which allows the synthesis of a large area and the control of the orientation of ZnO nanoparticles. It was possible to observe changes on the optical properties and surface morphology, which were attributed to both the spatial structure of the macromolecule and their interaction with the inorganic nanoparticles. It was also clear that hybrid porous matrices exhibit a blueshift with decreasing particle size.     

Radionuclide mapping of the Molise region (Central Italy) via gamma-ray spectrometry of soil samples: relationship with geological and pedological parameters

Radionuclide maps of the Molise region were created for the first time using gamma-ray spectrometry analysis of 205 soil samples. The geographical distributions of ⁴⁰K, ²³²Th and ²³⁸U were within the world average values for soils. ⁴⁰K was distributed homogeneously with a slight enhancement along the coastline. The decay chains of ²³⁸U and ²³²Th were in secular equilibrium with their daughters, also showing a homogeneous distribution except for localized areas of enhanced concentrations close to the borders with the Lazio and the Campania regions. Concentrations of all three radionuclides were correlated with geological and pedological characteristics of soils. The measured external gamma-dose rate in the air due to naturally occurring radionuclides in the soil, and the dose rate due to cosmic rays were in agreement with values measured in other Mediterranean regions. Increased ¹³⁷Cs levels from atmospheric nuclear weapons tests and the Chernobyl fallout were found at sites above 1,000 m a.s.l.     

High-Yield Synthesis of the Novel E,E-2,5-Dimethoxy-1,4-bis[2-(4-ethylcarboxylatestyril)]benzene by the Heck Reaction

The novel E,E-2,5-dimethoxy-1,4-bis[2-(4-ethylcarboxylatestyril)]benzene, 4, was obtained in good yield (92%), by the Heck cross-coupling reaction using Pd(dba)₂ and P(OPh)₃ like catalytic system. The high trans specificity of the product produced by the Heck reaction was confirmed by Fourier Transform–infrared and NMR. The methodology reported can be used as synthetic route for precursors to phenylenevinylene target systems with highly desired functional groups in their molecular structure, such as carboxylic, to build metal–organic frameworks and other applications within the supramolecular chemistry.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Controlling Aedes aegypti populations by limited Wolbachia‐based strategies in a seasonal environment

In this work, the linear feedback limited control strategy is proposed to indicate how the Wolbachia‐infected mosquitoes should be introduced in the seasonal environment to reduce the non‐Wolbachia mosquito population. The numerical simulations show that the proposed strategy reduces the population level of non‐Wolbachia mosquitos, avoiding mosquito spread and, consequently, reducing the number of cases of vector‐borne diseases.     

Donor-acceptor oligorotaxanes made to order

Five donor–acceptor oligorotaxanes made up of dumbbells composed of tetraethylene glycol chains, interspersed with three and five 1,5‐dioxynaphthalene units, and terminated by 2,6‐diisopropylphenoxy stoppers, have been prepared by the threading of discrete numbers of cyclobis(paraquat‐p‐phenylene) rings, followed by a kinetically controlled stoppering protocol that relies on click chemistry. The well‐known copper(I)‐catalyzed alkyne–azide cycloaddition between azide functions placed at the ends of the polyether chains and alkyne‐bearing stopper precursors was employed during the final kinetically controlled template‐directed synthesis of the five oligorotaxanes, which were characterized subsequently by ¹H NMR spectroscopy at low temperature (233 K) in deuterated acetonitrile. The secondary structures, as well as the conformations, of the five oligorotaxanes were unraveled by spectroscopic comparison with the dumbbell and ring components. By focusing attention on the changes in chemical shifts of some key probe protons, obtained from a wide range of low‐temperature spectra, a picture emerges of a high degree of folding within the thread protons of the dumbbells of four of the five oligorotaxanes—the fifth oligorotaxane represents a control compound in effect—brought about by a combination of C? H???O and π–π stacking interactions between the π‐electron‐deficient bipyridinium units in the rings and the π‐electron‐rich 1,5‐dioxynaphthalene units and polyether chains in the dumbbells. The secondary structures of a foldamer‐like nature have received further support from a solid‐state superstructure of a related [3]pseudorotaxane and density functional calculations performed thereon.     

Computational exploration of natural sunscreens

The photoprotective role of a family of compounds found in very different organisms is assessed by means of CASPT2//CASSCF computations. The potential use of these compounds in commercial applications in order to effectively dissipate light energy is explored.     

Unique Pt5 metallacycle: [Pt(II)Cl(pyrrolidinedithiocarbamate)]5

The neutral complex [PtCl(PyDT)](5) (PyDT = (CH(2))(4)NCS(2)(-)) represents the first example of a Pt(5) metallacycle. This unique architecture based on chiral S-bridged Pt(II) monomers was prepared by thermal degradation of the reaction product of PtCl(2) and a pyrrolidinedithioester.     

A novel α-isocyanoacetamide-based three-component reaction for the synthesis of dialkyl 2-acyl-5-aminofuran-3,4-dicarboxylates

α-Isocyanoacetamides, acyl chlorides and dialkylacetylenedicarboxylates undergo a smooth multicomponent reaction to produce dialkyl 2-acyl-5-aminofuran-3,4-dicarboxylates in good yield. The scope and mechanism of this new multicomponent transformation are discussed.