Three-Dimensional Fully pi-Conjugated Macrocycles: When Truly 3D-Aromatic and when 2D-Aromatic-in-3D?

Recently, several fully pi-conjugated macrocycles with strongly puckered or cage-type structures have been synthesized and found to exhibit aromatic character according to both experiments and computations. Herein, we examine their electronic structures and put them in relation to truly 3D-aromatic molecules (e.g., closo-boranes and certain charged fullerenes) as well as 2D-aromatic polycyclic aromatic hydrocarbons. We use qualitative theory combined with quantum chemical calculations, and find that the macrocycles explored thus far should be described as 2D-aromatic with three-dimensional structures (abbr. 2D-aromatic-in-3D) instead of truly 3D-aromatic. Besides fulfilling the 6n + 2 pi-electron rule, 3D-aromatic molecules with highly symmetric structures (e.g., Td and Oh) have a number of molecular orbital (MO) levels that are (at least) triply degenerate. At lower symmetries, the triple (or higher) orbital degeneracies should be kept in approximate sense. This last criterion is not fulfilled by macrocyclic cage molecules that are 2D-aromatic-in-3D. Their aromaticity results from a fulfillment of Hückel’s 4n + 2 rule for each individual macrocyclic path, yet, their pi-electron counts are coincidentally 6n + 2 numbers for macrocycles with three tethers of equal lengths. We instead link the 3D-macrocyclic molecules explored earlier to naphthalene, motivating their description as 2D-aromatics albeit with 3D structures. It is notable that macrocyclic cages which are 2D-aromatic-in-3D can be aromatic also when the tethers are of different lengths, i.e., when their pi-electron counts differ from 6n + 2. Finally, we identify tetrahedral and cubic pi-conjugated molecules that fulfill the 6n + 2 rule and which exhibit significant electron delocalization. Yet, their properties are similar to those of analogous compounds with electron counts that differ from 6n + 2. Thus, despite that these tetrahedral and cubic molecules show substantial pi-electron delocalization they should not be classified as true 3D-aromatics.

indexGIXS – software for visualizing and interactive indexing of grazing-incidence scattering data

Grazing incidence small- and wide-angle scattering (GISAXS, GIWAXS) are widely applied for the study of organic thin films, be it for the characterization of nanostructured morphologies in block copolymers, nanocomposites, or nanoparticle assemblies, or the packing and orientation of small aromatic molecules and conjugated polymers. Organic thin films typically are uniaxial powders, with specific crystallographic planes oriented parallel to the substrate surface. The associated fiber texture scattering patterns are complicated by refraction corrections and multiple scattering. We present an interactive graphics tool to index such patterns.

Resonance Raman Spectroscopy Investigation of the Interaction of Molecules Adsorbed on Solid Acid Surfaces

Many solid acids with very strong acid sites, as some zeolites, transition metal exchanged montmorillonites, sulfated metallic oxides, are known to have the oxidizing ability, which can be related to the catalytic activity of these materials. The interaction of these solid acids with aromatic molecules can give rise to several oxidation products. Intermediate species of aromatic molecules formed by interaction with strong solid acids had been reported, as radical cations, proving the oxidizing ability of the solids. Besides radical cations, charge transfer complexes between the solid acids and aromatic molecules can be formed. These radical cations and charge transfer complexes usually show absorption bands in the visible region, opening the possibility of studying these species by Resonance Raman Spectroscopy (RRS). Benzene and substituted benzenes, phenothiazine, t-stilbene, adsorbed on solid acids, are examples of molecules that had been investigated by RRS. Exciting the spectrum with suitable radiation makes it possible to observe the RRS of the species of interest even when its concentration is low, because of the preferential enhancement of the vibrational modes of the chromophore. A review of RRS studies of molecules adsorbed on solid acids is presented. RRS proved valuable in characterizing intermediate species as radical cations or charge transfer complexes formed on the solid acids.

Hyper-crosslinked polymers with controlled multiscale porosity for effective removal of benzene from cigarette smoke

A series of hyper-crosslinked polymers (HCPs) with connected hierarchical porous structures were synthesized from phenyl-based precursors of benzene (BEN), benzyl alcohol, aniline, biphenyl, and 1,3,5-triphenylbenzene (TPB) via the knitting method. The porous structures of the HCPs were greatly influenced by substituent groups and BEN ring number in the precursors. HCPs prepared from TPB had the largest surface area and pore volume with multiscale porosity. The porous structure of the HCPs could also be adjusted by the crosslinker amount. Insufficient crosslinking led to incomplete pore architecture, while excessive crosslinking resulted in a considerable decrease in the pore volume. With these HCPs as adsorbents, the BEN yield in the cigarette smoke could be largely reduced due to the connected multiscale porosity and π–π aromatic stacking interaction that facilitated the smoke aerosol passing and the small aromatic molecules absorbing, showing great potential of these HCPs as adsorbents for effective removal of BEN from cigarette smoke.

Parallel-stacked aromatic molecules in hydrogen-bonded inorganic frameworks

By precisely constructing molecules and assembling these into well-defined supramolecular structures, novel physical properties and functionalities can be realized, and new areas of the chemical space can be accessed. In both materials science and biology, a deeper understanding of the properties and exploitation of the reversible character of weak bonds and interactions, such as hydrogen bonds and π–π interactions, is anticipated to lead to the development of materials with novel properties and functionalities. We apply the hydrogen-bonded organic frameworks (HOFs) strategy to inorganic materials science using the cubic octamer of orthosilicic acid, [Si8O12][OH]8, as a building block, and find that various types of hydrogen-bonded inorganic frameworks (HIFs). We succeed in parallel π-stacking pure benzene, thiophene, selenophene, p-benzoquinone, thiophene·p-benzoquinone, and benzene·p-benzoquinone polymers infinitely. These polymers interact via their π-systems by taking advantage of the flexible pores of the three-dimensional nano-honeycomb HIFs, which consist of periodic wide and narrow segments.

Age-old transformation of oil hydrocarbons in polluted Grey-Brown Soil in the Absheron Peninsula

Oil production, transportation and refining are a source of the extensive environmental pollution. The study of oil pollutants allows the identification of their behavior pattern necessary in order to elaborate efficient decontamination technologies. The Absheron oil field is one of the most long-term exploited deposit in the world. Today this area is a unique place to investigate the long-lasting natural oil transformation processes. Grey-Brown Soils contaminated with crude oil 100 and 40 years ago and currently were investigated. Hexane-extractable fraction of oil compounds was examined by chemical methods, gas chromatography and mass spectrometry. In the process of natural degradation, molecular weight of oil hydrocarbons and degree of oxidation significantly increased, while the contents of carbon and hydrogen slightly decreased with time. The results obtained have shown the accumulation of high-molecular weight aromatic molecules with high degree of unsaturation in the upper layer of the soil contaminated 100 years ago. These aromatic structures exhibit the great resistance to decomposition and may be carcinogenic, thus posing a risk to human health. The contamination with oil resulted in altering soil properties. More pronounced change was observed in the soil carbon, including the soil contaminated 100 years ago. Over time after contamination, the soil alkalinity enhanced, whereas soil pH did not change. Our study evidences that oil pollutants continue to be present and the soil properties have not recovered even 100 years after pollution. Reclamation of these areas requires the application of special technologies.

Occurrence of Double Bond in π-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal Structures

A chemical bonding of several metallabenzenes and metallabenzynes was studied via an adaptive natural density partitioning (AdNDP) algorithm and the induced magnetic field analysis. A unique chemical bonding pattern was discovered where the M=C (M: Os, Re) double bond coexists with the delocalized 6c-2e π-bonding elements responsible for aromatic properties of the investigated complexes. In opposition to the previous description where 8 delocalized π-electrons were reported in metallabenzenes and metallabenzynes, we showed that only six delocalized π-electrons are present in those molecules. Thus, there is no deviation from Hückel’s aromaticity rule for metallabenzynes/metallabenzenes complexes. Based on the discovered bonding pattern, we propose two thermodynamically stable novel molecules that possess not only π-delocalization but also retain six σ-delocalized electrons, rendering them as doubly aromatic species. As a result, our investigation gives a new direction for the search for carbon-metal doubly aromatic molecules.

Hybrid Sol-Gel Surface-Enhanced Raman Sensor for Xylene Detection in Solution

This paper reports on the fabrication and characterization of a plasmonic/sol-gel sensor for the detection of aromatic molecules. The sol-gel film was engineered using polysilsesquioxanes groups to capture the analyte, through π-π interaction, and to concentrate it close to the plasmonic surface, where Raman amplification occurs. Xylene was chosen as an analyte to test the sensor. It belongs to the general class of volatile organic compounds and can be found in water or in the atmosphere as pollutants released from a variety of processes; its detection with SERS is typically challenging, due to its low affinity toward metallic surfaces. The identification of xylene was verified in comparison with that of other aromatic molecules, such as benzene and toluene. Investigations were carried out on solutions of xylene in cyclohexane, using concentrations in the range from 0 to 800 mM, to evaluate the limit of detection (LOD) of about 40 mM.

Characterization Techniques Coupled With Mathematical Tools for Deepening Asphaltenes Structure

Asphaltenes constitute a heavy fraction of fossil fuels and their characterization is still a very difficult and challenging issue due to their complex and variable composition. Asphaltene components are highly condensed aromatic molecules having some heteroatom and aliphatic functionalities. Their molecular weights distribution span a wide range, from hundreds to millions of units, in dependence on the diagnostic used, leading to speculation about possible occurrence of self-aggregation. In the present work, mass spectrometry, with properly developed mathematical methods, size ex-clusion chromatography and X-ray diffraction analysis have been applied to asphaltenes for giving some further insight on their MW distribution and characteristics. The results here reported give further quantitative support to the experimental data interpretation already reported in previous works.

Modified Red Muds and Slag Based Hydraulic Binders for Zn Removal: A Matrix-Spiking Approach Applied on Clayey Sediments

Dredging sediments can be implemented as primary resources in several civil engineering applications, on the condition that the release of anthropogenic compounds meets environmental requirements. The remediation of sedimentary wastes constitutes therefore, a key step before valorization consideration in circular economy schemes. This study focused on Zn removal from clayey river sediments dredged in northern France (Lille, Saint-Omer and Aire-Sur-La Lys) using a Thermo-Evolved Red Mud (TERM) and a Slag Based Hydraulic Binder (SBHB). The first step consisted in investigating Zn-trapping mechanisms prior to TERM and SBHB application as Zn-stabilizers. Results underlined poorer metal retention within the most organic sediment (high fatty acids and polycyclic aromatic molecules concentrations), emphasizing the minor role of the organic fraction typology during Zn-trapping. The pollutant displayed its best binding yields within the sediment with the highest interstitial pH and specific areas, which stressed out the preponderant influence of alkalinization ability and particles size distribution. In a second step, the spiked sediments were treated with TERM and SBHB, which resulted in a substantial lowering of Zn release at 12% of stabilizer/sediment ratio. Even though the organic content role was not preeminent during the pollutant trapping, it appeared here influential as delays in removal efficiencies were observed for the most endowed sediment. Two preferential geochemical pathways were adopted during the remediation operations with significant promotive roles of basic background pH. Indeed, Zn removal with TERM consisted mainly in sorptive mechanisms involving exchanges with Ca and Mg ions, whereas binding onto SBHB was principally achieved through precipitation phenomena.