Diradical B/N-Doped Polycyclic Hydrocarbons

Heterocyclic diradicaloids with atom-precise control over open-shell nature are promising materials for organic electronics and spintronics. Herein, we disclose quinoidal π-extension of a B/N-heterocycle for generating B/N-type organic diradicaloids. Two quinoidal π-extended B/N-doped polycyclic hydrocarbons that feature fusion of the B/N-heterocycle motif with the antiaromatic s-indacene or dicyclopenta[b,g]naphthalene core were synthesized. This quinoidal π-extension and B/N-heterocycle leads to their open-shell electronic nature, which stands in contrast to the multiple-resonance effect of conventional B/N-type emitters. These B/N-type diradicaloids have modulated (anti)aromaticity and enhanced diradical characters comparing with the all-carbon analogues, as well as intriguing properties, such as magnetic activities, narrow energy gaps and highly red-shifted absorptions. This study thus opens the new space for both of B/N-doped polycyclic π-systems and heterocyclic diradicaloids.     

Design Strategies for Diradical Boron/Nitrogen Doped Carbon-Based Materials

New heterocyclic diradicaloids based on boron and nitrogen-doped polycyclic systems with open-shell ground-states are obtained via concomitant structural and quinoidal extensions, thus allowing to merge the best of both design strategies. A combination of experimental characterization and theoretical calculations have helped disclose their electronic structure, as well as rationalize their associated magnetic and photophysical properties, spanning the chemical space of available molecular templates for cutting-edge applications in organic electronics and spintronics.     

Modular Synthesis of Structurally Diverse Azulene-Embedded Polycyclic Aromatic Hydrocarbons by Knoevenagel-Type Condensation

The research interest in azulene-embedded polycyclic aromatic hydrocarbons (PAHs) has significantly increased recently, but the lack of efficient synthetic strategies impedes the investigation of their structure-property relationships and further opto-electronic applications. Here we report a modular synthetic strategy towards diverse azulene-embedded PAHs by a tandem Suzuki coupling and base-promoted Knoevenagel-type condensation with good yields and great structural versatility, including non-alternant thiophene-rich PAHs, butterfly- or Z-shaped PAHs bearing two azulene units, and the first example of a two-azulene-embedded double [5]helicene. The structural topology, aromaticity and photophysical properties were investigated by NMR, X-ray crystallography analysis and UV/Vis absorption spectroscopy assisted by DFT calculations. This strategy provides a new platform for rapidly synthesizing unexplored non-alternant PAHs or even graphene nanoribbons with multiple azulene units.     

Cascade Synthesis of Benzotriazulene with Three Embedded Azulene Units and Large Stokes Shifts

We report here the one-pot synthesis of benzo[1,2-a : 3,4-a′ : 5,6-a′′]triazulene ( BTA ), wherein three azulene units are embedded through a tandem reaction comprising two steps, Suzuki coupling and Knoevenagel condensation, between a readily available triborylated truxene precursor and 8-bromo-1-naphthaldehyde. Its nitration leads to a regioselective trinitrated product, namely, BTA - NO₂ . Single-crystal X-ray crystallography revealed that the superstructure of BTA consists of a dimer stacked by two enantiomeric helicene conformers, while that of BTA - NO₂ consists of an unprecedented π-tetramer stacked from two enantiomeric dimers, that is, four distinct helicene conformers. Both compounds show excellent stability and fluorescence with large Stokes shifts of up to 5100 cm⁻¹. In addition, BTA - NO₂ exhibits a unique solvatochromic effect in different solvents and hydrogen-bonding-induced emission transfer in different ratios of THF/H₂O solutions.     

Dinor[7]helicene and Beyond: Divergent Synthesis of Chiral Diradicaloids with Variable Open-Shell Character

Diradicaloid helicenes constructed formally by non-benzenoid double π-extension of phenanthrene were synthesized by a common strategy involving double electrophilic benzannulation. Steric effects in the second benzannulation step led to considerable structural diversity among the products, yielding a symmetrical dinor[7]helicene 1 and two isomeric unsymmetrical double helicenes 2 and 3 , containing a nor[5]helicene and [4]helicene fragment, respectively, in addition to a common nor[6]helicene motif. Geometries, configurational dynamics, and electronic structure of these helicenes were analyzed using solid-state structures, spectroscopic methods, and computational analyses. The open-shell character of the singlet states of these helicenes increases in the order 3 < 1 < 2 , with strongly varying diradicaloid indexes and singlet–triplet gaps. Compounds 1 – 3 displayed narrow optical gaps of 0.79–1.25 eV, resulting in significant absorption in the near infrared (NIR) region. They also exhibit reversible redox chemistry, each of them yielding stable radical cations, radical anions, and dianions, in some cases possessing intense NIR absorptions extending beyond 2500 nm.     

S-shaped para-Quinodimethane-Embedded Double [6]Helicene and Its Charged Species Showing Open-Shell Diradical Character

Helicenes and extended helical π-conjugated compounds have been widely studied, but most of the systems contain only aromatic benzene or heterocyclic rings, showing local aromatic character. Herein, new S-shaped double [6]helicene 1 , which has two embedded para-quinodimethane (p-QDM) units, is reported. Due to the existence of a proaromatic quinoidal substructure, it has open-shell diradical character. Its model compound, C-shaped single [6]helicene 2 containing one p-QDM unit, was also synthesized and compared. Their ground-state structures and electronic properties were systematically studied by a combination of various experimental methods assisted by theoretical calculations. Compound 1 has a double-helical structure in the crystal, with the two terminal [6]helicene units bent in opposite directions (i.e., anti form). However, an anti/syn isomerization process with a moderate interconversion energy barrier was observed on the NMR timescale. Compound 1 shows amphoteric redox behavior. It also exhibits open-shell diradical character (y₀=12.1 %) and a small singlet–triplet gap. On the other hand, compound 2 has a typical closed-shell nature. The dication and dianion of 1 also show open-shell diradical character. The dianion of 2 and the tetraanion of 1 exhibit similar electronic structures to their respective isoelectronic structures, that is, [6]helicene and a double [6]helicene. This work provides some insights into the design and synthesis of stable helical π systems with open-shell diradical character and magnetic activity.     

ChemInform Abstract: Singlet Diradical Character of S2N2.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Determination of polycyclic aromatic hydrocarbon metabolites in milk by a quick,easy, cheap,effective, rugged and safe extraction and capillary electrophoresis

We describe the first application of a quick, easy, cheap, effective, rugged and safe extraction technique to the CZE analysis of monohydroxylated metabolites of polycyclic aromatic hydrocarbons in milk. Complete resolution of 2‐hydroxyfluorenene, 1‐hydroxynaphthalene, 2‐hydroxynaphthalene, 3‐hydroxyphenanthrene, and 9‐hydroxyphenanthrene was accomplished in 4 min of electrophoretic run. Limits of detection at the parts‐per‐billion were obtained with a single solvent (acetonitrile) for metabolite extraction and sample stacking. The small sample volume (1.2 mL) and the conservative usage of chemicals provided a simple and rapid procedure for the simultaneous extraction of numerous samples. Adding 4 min of electrophoretic run per sample, it should be possible to screen ten samples in approximately 1 h of analysis time. The nanoliter extract volume required for sample injection allows for further chromatographic usage and confirmation of positive samples. The unique electrophoretic pattern of the studied metabolites demonstrates the potential for the unambiguous determination of positional isomers with very similar chromatographic behaviors and undistinguishable mass fragmentation patterns.     

Circumcoronenes

Circumcoronene, a hexagonal graphene fragment with six zigzag edges, has been the focus of theoretical studies for many years, but its synthesis in solution has remained a challenge. In this study, we present a facile method for synthesizing three derivatives of circumcoronene using Brønsted/Lewis acid-mediated cyclization of vinyl ether or alkyne. Their structures were confirmed through X-ray crystallographic analysis. Bond length analysis, NMR measurement, and theoretical calculations showed that circumcoronene mostly follows Clar's bonding model and exhibits dominant local aromaticity. Its absorption and emission spectra are similar to those of the smaller hexagonal coronene due to its six-fold symmetry.     

气相色谱-质谱联用法测定橡胶制品中多环芳烃（蒽）含量不确定度评定

目的对气相色谱-质谱联用仪法测定橡胶制品中多环芳烃（蒽）含量不确定度进行评定,确定影响不确定度的关键因素。方法依据《ZEK01.4-2008 GS认证过程中PAHs的测试和验证》,使用气相色谱-质谱联用仪法测定橡胶制品中多环芳烃（蒽）含量,并对结果的不确定度进行评定,分析影响测量不确定度的各个因素,对各个分量进行计算和合成。结果扩展不确定度U=5.7 mg/kg,置信概率95%。结论该实验的不确定度主要影响因素是曲线校准。     

A Crowning Achievement: The First Solution-Phase Synthesis of Circumcoronenes

Circumcoronene is a highly symmetric polybenzenoid hydrocarbon that has fascinated organic chemists and materials scientists for decades. However, until recently, it had only been studied theoretically, because its synthesis in solution remained challenging. In a recent report, Wu and co-workers described the first successful solution-phase synthesis and isolation of crystalline circumcoronene derivatives, validating the long-predicted Clar structure. Their synthetic approach enables preparation of new polycyclic benzenoid hydrocarbons with multiple K-regions, which are difficult to obtain, and expands our understanding of the chemistry of these systems.     

土壤中多环芳烃修复技术的研究进展

近年来我国的土壤污染问题日益严重,严重危害着人类的生活环境与身体健康,其中主要的有机污染物之一为多环芳烃(PAHs)。PAHs作为一种持久性有机污染物在全球范围内广泛存在,其主要污染来源于人为因素。由于PAHs复杂的杂环芳环结构、较强的疏水性和较高的热稳定性等,使其在土壤中不易自然降解因而具有较高的持久性。本文综述PAHs的主要污染来源、暴露途径及其对人体的危害,并从物理、化学和生物三个方面简要介绍土壤中PAHs的修复方法,并分析每种方法的优势以及面临的挑战。新兴的修复技术结合三种修复技术的优点,具有更好的修复效果和应用前景,但仍存在着一些亟待解决的问题。期望本文能为土壤中PAHs的修复提供借鉴,并为今后的研究方向提供新的思路。     

Trap and Desorption Gc/Ms for Detection Polycyclic Aromatic Hydrocarbons in Motorcycles Emission

ABSTRACT

The application of trap and desorption GC/MS to monitoring of sixteen PAHs in the exhaust emissions from motorcycles was investigated. The time of sampling and analysis for one sample is in 40 minutes. The relative standard deviations were estimated from 20% to 34% for monitoring the total concentrations of PAHs from the emissions of motorcycles. The PAH concentrations appeared to show distinct variations with the stroke, engine size and the aging of motorcycles. The predominate of PAHs in the emissions of motorcycle were naphthalene, fluorene, anthracene, fluoranthene and pyrene. Naphthalene exhibited the highest concentration that was obtained over 79% of the total concentration of sixteen PAHs in the emissions of the over nine years old motorcycles.     

Polycyclic Aromatic Hydrocarbon Burden in Fruit and Vegetable Species Cultivated in Allotments in an Industrial Area

The polycyclic aromatic hydrocarbon (PAH) burden of various fruit and vegetable species (strawberries, apples, tomatoes, lettuce, kohlrabi, potatoes, parsley and kale) cultivated in allotments in the industrial area of Bitterfeld-Wolfen (Germany) were determined. In addition, the garden soils of the sampling sites were analysed. The total PAH concentrations of fruit and vegetables investigated varied in the range of 1-120 µg/kg fresh weight, with the highest being found in parsley and kale. As the highest concentration of benzo(a)pyrene (BaP) was 0.55 µg/kg in a parsley sample, none of the samples exceeded the recommended BaP limit in vegetable foods of 1 µg/kg. A positive relationship between the total PAH burden and the cultivating site was only found for the more highly contaminated species parsley and kale. The total PAH concentrations in the garden soils ranged from 28 to about 7000 µg/kg dry weight.     

Ozone Degradation of Polycyclic Aromatic Hydrocarbons Adsorbed on Asbestos

Abstract

The polycyclic aromatic hydrocarbons (PAH) represent a major source of pollution. The adsorption properties of chrysotile give us a good application as an asbestos filter and the regeneration can be made by ozonolysis for a complete destruction to non toxic compounds.     

Synthesis of a π-Extended Double [9]Helicene

Double helicenes are appealing chiral frameworks. Their π-extension is desirable to achieve (chir)optical response in the visible and near-infrared (NIR) region, but access to higher double [n]helicenes (n≥8) has remained challenging. Herein, we report an unprecedented π-extended double [9]helicene ( D9H ), unambiguously revealing its structure by single-crystal X-ray diffraction. D9H shows remarkable NIR emission from 750 to 1100 nm with a high photoluminescence quantum yield of 18 %. In addition, optically pure D9H exhibits panchromatic circular dichroism with a notable dissymmetry factor (g_CD) of 0.019 at 590 nm, which is among the highest in the visible region for reported helicenes.     

Enhanced Gain in Organic Photodetectors Using the Polymer with Singlet Open-Shell Ground State

Photodetectors are critical components in intelligent optoelectronic systems, and photomultiplication-capable devices are essential for detecting weak optical signals. Despite significant advances, developing photomultiplication-type organic photodetectors with high gain and low noise current simultaneously remains challenging. In this work, a new conjugated polymer PDN with singlet open-shell ground state is introduced in active layers for electron capture, and the corresponding PDN-based photodetectors exhibited an enhanced photoelectric gain and decreased dark current density at a low forward bias. At 1.5 V, the PDN-based ternary photodetector has the external quantum efficiency (EQE) up to 2552.3 % and the specific detectivity of 1.4×10¹⁴ Jones at 710 nm calculated by the measured noise current, with the gain 22 times higher than that of the control group. This study provides an approach for exploiting polymers with singlet open-shell ground state to enhance the gain of organic photodetectors.     

Rearrangements in Scholl Reaction

Rearrangements in Scholl reaction are mostly serendipitous. The design of molecular precursors is what seems to guide the course of rearrangement. This review consolidates different classes of precursors used in Scholl reaction and their accompanying rearrangements that include aryl migration, migration followed by cyclization and skeletal rearrangements involving ring expansion, ring contraction and both, under the reaction conditions. The attempt in collating heretofore-reported examples in this review is to guide designing appropriate precursors to predictably achieve complex molecular structures or nanographenes or defect-nanographenes via rearrangement.     

Unconventional Pathway in the Gas-Phase Synthesis of 9H-Fluorene (C13H10) via the Radical–Radical Reaction of Benzyl (C7H7) with Phenyl (C6H5)

The simplest polycyclic aromatic hydrocarbon (PAH) carrying a five-membered ring—9H-fluorene (C₁₃H₁₀)—is produced isomer-specifically in the gas phase by reacting benzyl (C₇H₇⋅) with phenyl (C₆H₅⋅) radicals in a pyrolytic reactor coupled with single photon ionization mass spectrometry. The unconventional mechanism of reaction is supported by theoretical calculations, which first produces diphenylmethane and unexpected 1-(6-methylenecyclohexa-2,4-dienyl)benzene intermediates (C₁₃H₁₂) accessed via addition of the phenyl radical to the ortho position of the benzyl radical. These findings offer convincing evidence for molecular mass growth processes defying conventional wisdom that radical-radical reactions are initiated through recombination at their radical centers. The structure of 9H-fluorene acts as a molecular building block for complex curved nanostructures like fullerenes and nanobowls providing fundamental insights into the hydrocarbon evolution in high temperature settings.     

Benzonorcorrole NiII Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo‐Fusion

Fused benzene rings to antiaromatic compounds generally improve their stability but attenuate their antiaromaticity. The opposite case is now reported. Ni^II benzonorcorroles were synthesized and the effect of benzo‐fusion on the antiaromaticity was elucidated. The benzo‐fusion resulted in significant decrease of the HOMO–LUMO gaps and enhancement of the paratropic ring current effect. Furthermore, the introduction of the benzo groups induced singlet diradical character in the antiaromatic porphyrinoid.