The Counterion Effect on the Assembly of Coordination Networks of Cationic (η3‐Allyl)palladium Complexes Containing 3,5‐Dimethyl‐4‐nitro‐1H‐pyrazole

Two new (η³‐allyl)palladium complexes containing the ligand 3,5‐dimethyl‐4‐nitro‐1H‐pyrazole (Hdmnpz) were synthesized and characterized as [Pd(η³‐C₃H₅)(Hdmnpz)₂]BF₄ ( 1 ) and [Pd(η³‐C₃H₅)(Hdmnpz)₂]NO₃ ( 2 ). The structures of these compounds were determined by single‐crystal X‐ray diffraction to evaluate the intermolecular assembly. Each complex exhibits similar coordination behavior consistent with cationic entities comprised of two pyrazole ligands coordinated with the [Pd(η³‐C₃H₅)]⁺ fragment in an almost square‐planar coordination geometry. In 1 , the cationic entities are propagated through strong intermolecular H‐bonds formed between the pyrazole NH groups and BF ions in one‐dimensional polymer chains along the a axis. These chains are extended into two‐dimensional sheet networks via bifurcated H‐bonds. New intermolecular interactions established between NO₂ and Me substituents at the pyrazole ligand of neighboring sheets give rise to a three‐dimensional network. By contrast, compound 2 presents molecular cyclic dimers formed through N? H???O H‐bonds between two NO counterions and the pyrazole NH groups of two cationic entities. The dimers are also connected to each other through C? H???O H‐bonds between the remaining O‐atom of each NO ion and the allyl CH₂ H‐atom. Those interactions expand in a layer which lies parallel to the face (101).     

Quotient polytopes of cyclic polytopes part II: Stability of thef-vector and of thek-skeleton

This paper is the continuation of an earlier paper on quotient polytopesC(v, 2m)/F of cyclic polytopes and the associated quotient complexesC(V, 2m)/J. Here, we study mainly what changes in the faceJ do not affect thef-vector of the quotientC(V, 2m)/J. In the last section we examine the corresponding question fork-skeleta, i.e., what changes inJ do not affect the isomorphism type of skel _k C(V, 2m)/J.     

Sorting out the value of spectroscopic tools to assess the Colletotrichum acutatum impact in olive cultivars with different susceptibilities

The olive tree (Olea europaea L.) can be affected by Colletotrichum acutatum, causing a loss of yield and quality of the final products, whilst the incidence of this fungal infection depends on several factors, including cultivar susceptibility. Thus, the effect of C. acutatum infection in cultivars displaying different susceptibilities to this fungal disease (‘Galega Vulgar’ ‐ susceptible, ‘Cobrançosa’ ‐ moderately susceptible, ‘Picual’ ‐ tolerant) has been assessed through spectrophotometric methods and HPLC, while the FTIR spectra of the cuticles have been concomitantly registered, resorting to the ATR accessory. With the support of multivariate analysis, these spectra allowed to discriminate olives with distinct infection times, besides retrieving evidences concerning the different susceptibility of each cultivar, while these observations were reinforced by the spectrophotometric and chromatographic methods. Furthermore, the assessment of the phenolic profile evidenced individual compounds in the distinct cultivars, so as their variations in response to the fungal infection.     

Quotient polytopes of cyclic polytopes part I: Structure and characterization

We investigate the quotient polytopesC/F, whereC is a cyclic polytope andF is a face ofC. We describe the combinatorial structure of such quotients, and show that under suitable restrictions the pair (C, F) is determined by the combinatorial type ofC/F. We describe alternative constructions of these quotients by “splitting vertices” of lower-dimensional cyclic polytopes. Using Gale diagrams, we show that every simpliciald-polytope withd+3 vertices is isomorphic to a quotient of a cyclic polytope.     

Synthesis of a Helical Bilayer Nanographene

A rigid, inherently chiral bilayer nanographene has been synthesized as both the racemate and enantioenriched M isomer (with 93 % ee) in three steps from established helicenes. This folded nanographene is composed of two hexa‐peri‐hexabenzocoronene layers fused to a [10]helicene, with an interlayer distance of 3.6 Å as determined by X‐ray crystallography. The rigidity of the helicene linker forces the layers to adopt a nearly aligned AA‐stacked conformation, rarely observed in few‐layer graphene. By combining the advantages of nanographenes and helicenes, we have constructed a bilayer system of 30 fused benzene rings that is also chiral, rigid, and remains soluble in common organic solvents. We present this as a molecular model system of bilayer graphene, with properties of interest in a variety of potential applications.     

Inside Back Cover: Electronic Control of the Scholl Reaction: Selective Synthesis of Spiro vs Helical Nanographenes (Angew. Chem. Int. Ed. 7/2023)

Scholl oxidation has become an essential reaction in the bottom-up synthesis of molecular nanographenes. Herein, we describe a Scholl reaction controlled by the electronic effects on the starting substrate ( 1 a , b ). Anthracene-based polyphenylenes lead to spironanographenes under Scholl conditions. In contrast, an electron-deficient anthracene substrate affords a helically arranged molecular nanographene formed by two orthogonal dibenzo[fg,ij]phenanthro-[9,10,1,2,3-pqrst]pentaphene (DBPP) moieties linked through an octafluoroanthracene core. Density Functional Theory (DFT) calculations predict that electronic effects control either the first formation of spirocycles and subsequent Scholl reaction to form spironanographene 2 , or the expected dehydrogenation reaction leading solely to the helical nanographene 3 . The crystal structures of four of the new spiro compounds (syn 2 , syn 9 , anti 9 and syn 10 ) were solved by single crystal X-ray diffraction. The photophysical properties of the new molecular nanographene 3 reveal a remarkable dual fluorescent emission.     

Sets in a euclidean space which are not a countable union of convex subsets

We prove that if a closed planar setS is not a countable union of convex subsets, then exactly one of the following holds:

Theoretical Investigations of the Effect of a Homologous Series of Anionic Surfactants on the Metabolism Bioactivity of Chromobacterium violaceum

Theoretical calculations were performed to obtain physicochemical properties associated with the effect of homologous anionic n-alkylsulfate surfactants on the metabolism of Chromobacterium violaceum. The quantitative experimental effects on the respiration process were those obtained from calorimetric data and were used to correlate the Structure–Activity–Relationship (SAR) of these compounds. Semiempirical AM1 and ab initio DFT levels, employing the set CEP-31G, were used for the theoretical calculations and were parameterized using the continuum-solvation model COSMO for solvent contributions. Chemometric analyses (HCA: hierarchical cluster analysis and PCA: principal component analysis) were used to correlate the physicochemical properties of these compounds and their biological activities. The results indicate that the biological activities of these compounds increase as the hydrocarbon chain length, volume, molar volume and exothermic enthalpy of formation (Δ_f H ^∘) increase; in contrast they decrease with decreases of the solvent effect (SE), ionization enthalpy (IE) and HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies.     

Ball polytopes and the Vázsonyi problem

Let V be a finite set of points in the Euclidean d-space (d ≧ 2). The intersection of all unit balls B(υ, 1) centered at υ, where υ ranges over V, henceforth denoted by $ \mathcal{B} $ (V) is the ball polytope associated with V. After some preparatory discussion on spherical convexity and spindle convexity, the paper focuses on two central themes. (a) Define the boundary complex of $ \mathcal{B} $ (V), i.e., define its vertices, edges and facets in dimension 3, and investigate its basic properties. (b) Apply results of this investigation to characterize finite sets of diameter 1 in the (Euclidean) 3-space for which the diameter is attained a maximal number of times as a segment (of length 1) with both endpoints in V. A basic result for such a characterization goes back to Grünbaum, Heppes and Straszewicz, who proved independently of each other, in the late 1950’s by means of ball polytopes, that the diameter of V is attained at most 2|V| ? 2 times. Call V extremal if its diameter is attained this maximal number (2|V| ? 2) of times. We extend the aforementioned result by showing that V is extremal iff V coincides with the set of vertices of its ball polytope $ \mathcal{B} $ (V) and show that in this case the boundary complex of $ \mathcal{B} $ (V) is self-dual in some strong sense. The problem of constructing new types of extremal configurations is not addressed in this paper, but we do present here some such new types.