APEX Strategy Represented by Diels–Alder Cycloadditions—New Opportunities for the Syntheses of Functionalised PAHs

Diels–Alder cycloaddition of various dienophiles to the bay region of polycyclic aromatic hydrocarbons (PAHs) is a particularly effective and useful tool for the modification of the structure of PAHs and thereby their final properties. The Diels–Alder cycloaddition belongs to the single-step annulative π-extension (APEX) reactions and represents the maximum in synthetic efficiency for the constructions of π-extended PAHs including functionalised ones, nanographenes, and π-extended fused heteroarenes. Herein we report new applications of the APEX strategy for the synthesis of derivatives of 1,2-diarylbenzo[ghi]perylene, 1,2-diarylbenzo[ghi]perylenebisimide and 1,2-disubstituted-benzo[j]coronene. Namely, the so far unknown cycloaddition of 1,2-diarylacetylenes into the perylene and perylenebisimide bay regions was used. 1,2-Disubstituted-benzo[j]coronenes were obtained via cycloaddition of benzyne into 1,2-diarylbenzo[ghi]perylenes by using a new highly effective system for benzyne generation and/or high pressure conditions. Moreover, we report an unprecedented Diels–Alder cycloaddition–cycloaromatisation domino-type reaction between 1,4-(9,9-dialkylfluoren-3-yl)-1,3-butadiynes and perylene. The obtained diaryl-substituted core-extended PAHs were characterised by DFT calculation as well as electrochemical and spectroscopic measurements.     

A sequential cyclization/π-extension strategy for modular construction of nanographenes enabled by stannole cycloadditions

The synthesis of polycyclic aromatic hydrocarbons (PAHs) and related nanographenes requires the selective and efficient fusion of multiple aromatic rings. For this purpose, the Diels–Alder cycloaddition has proven especially useful; however, this approach currently faces significant limitations, including the lack of versatile strategies to access annulated dienes, the instability of the most commonly used dienes, and difficulties with aromatization of the [4 + 2] adduct. In this report we address these limitations via the marriage of two powerful cycloaddition strategies. First, a formal Cp₂Zr-mediated [2 + 2 + 1] cycloaddition is used to generate a stannole-annulated PAH. Secondly, the stannoles are employed as diene components in a [4 + 2] cycloaddition/aromatization cascade with an aryne, enabling π-extension to afford a larger PAH. This discovery of stannoles as highly reactive – yet stable for handling – diene equivalents, and the development of a modular strategy for their synthesis, should significantly extend the structural scope of PAHs accessible by a [4 + 2] cycloaddition approach.

Stannoles are introduced as a new, spontaneously aromatizing diene for [4 + 2] cycloadditions that can be easily introduced into diverse conjugated systems, facilitating the efficient synthesis of complex PAHs and their π-extension.     

Evaluation of Polycyclic Aromatic Hydrocarbons in Smoked Cheeses Made in Poland by HPLC Method

Smoked cheeses are particularly popular among consumers for their flavor and aroma. Of interest, therefore, is the health aspect related to the likelihood of polycyclic aromatic hydrocarbons (PAHs), which are known carcinogens found in smoked products. Thus, the purpose of this study was to evaluate the occurrence of 15 polycyclic aromatic hydrocarbons (PAHs) in smoked and non-smoked cheeses purchased in Poland to monitor their safety. The level of selected PAHs in cheese samples was determined using the HPLC-DAD-FLD method. Most of the cheeses tested met the maximum level of benzo[a]pyrene (2 μg/kg) and the sum of benz[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene (12 μg/kg) established for these products. However, all the cheeses studied in this work had relatively low amounts of the sum of these compounds compared to the information available in the cheese literature, ranging from <LOD to 24.5 μg/kg. This amount does not pose a health risk to consumers. The predominant PAHs found were naphthalene, phenanthrene, fluorene and acenaphthene. Benzo[a]pyrene, the marker compound representing carcinogenic PAHs, was found in 100% and 0% of Polish smoked and non-smoked cheeses, respectively. Although there are currently no regulations for smoked cheeses and maximum concentrations of PAHs in this type of food product, control of PAHs content in cheeses is important due to the mutagenic and carcinogenic potential of these chemicals.     

Heart Failure and PAHs,OHPAHs, and Trace Elements Levels in Human Serum: Results from a Preliminary Pilot Study in Greek Population and the Possible Impact of Air Pollution

Cardiovascular diseases (CVDs) have been associated with environmental pollutants. The scope of this study is to assess any potential relation of polycyclic aromatic hydrocarbons (PAHs), their hydroxylated derivatives, and trace elements with heart failure via their direct determination in human serum of Greek citizens residing in different areas. Therefore, we analyzed 131 samples including cases (heart failure patients) and controls (healthy donors), and the respective demographic data were collected. Significantly higher concentrations (p < 0.05) were observed in cases’ serum regarding most of the examined PAHs and their derivatives with phenanthrene, fluorene, and fluoranthene being the most abundant (median of >50 μg L⁻¹). Among the examined trace elements, As, Cd, Cu, Hg, Ni, and Pb were measured at statistically higher concentrations (p < 0.05) in cases’ samples, with only Cr being significantly higher in controls. The potential impact of environmental factors such as smoking and area of residence has been evaluated. Specific PAHs and trace elements could be possibly related with heart failure development. Atmospheric degradation and smoking habit appeared to have a significant impact on the analytes’ serum concentrations. PCA–logistic regression analysis could possibly reveal common mechanisms among the analytes enhancing the hypothesis that they may pose a significant risk for CVD development.     

Synthesis of Rationally Halogenated Buckybowls by Chemoselective Aromatic C−F Bond Activation

Halogenated buckybowls or bowl‐shaped polycyclic aromatic hydrocarbons (BS‐PAHs) are key building blocks for the “bottom‐up” synthesis of various carbon‐based nanomaterials with outstanding potential in different fields of technology. The current state of the art provides quite a limited number of synthetic pathways to BS‐PAHs; moreover, none of these approaches show high selectivity and tolerance of functional groups. Herein we demonstrate an effective route to BS‐PAHs that includes directed intramolecular aryl–aryl coupling through C−F bond activation. The coupling conditions were found to be completely tolerant toward aromatic C−Br and C−Cl bonds, thus allowing the facile synthesis of rationally halogenated buckybowls with an unprecedented level of selectivity. This finding opens the way to functionalized BS‐PAH systems that cannot be obtained by alternative methods.     

Excited States Symmetry Breaking and In-Plane Polarization Cause Chiral Reversal in Diastereomers

In this work, we investigate the electronic transitions and chirality of three isomers of huge conjugated systems: asymmetric diastereomers (MMMM) and two symmetrical diastereomers (PMPM and PPMM). The physical mechanism of flipping has been studied theoretically. The new ribbon-shaped polycyclic aromatic hydrocarbons (PAHs) molecule is formed by connecting three graphene-like systems with large conjugated π orbitals. By calculating and analyzing electromagnetic interaction decomposition over distance, it can be found that the chirality reversal of different energies is caused by the symmetrical fracture of TMDM in the Z direction. The chirality reversal at the same energy is caused by the in-plane polarization of the TMDM along the Y direction.     

Aggregation caused quenching to aggregation induced emission transformation: a precise tuning based on BN-doped polycyclic aromatic hydrocarbons toward subcellular organelle specific imaging

Polycyclic aromatic hydrocarbons (PAHs) with boron–nitrogen (BN) moieties have attracted tremendous interest due to their intriguing electronic and optoelectronic properties. However, most of the BN-fused π-systems reported to date are difficult to modify and exhibit traditional aggregation-caused quenching (ACQ) characteristics. This phenomenon greatly limits their scope of application. Thus, continuing efforts to seek novel, structurally distinct and functionally diverse structures are highly desirable. Herein, we proposed a one-stone-two-birds strategy including simultaneous exploration of reactivity and tuning of the optical and electronic properties for BN-containing π-skeletons through flexible regioselective functionalization engineering. In this way, three novel functionalized BN luminogens (DPA-BN-BFT, MeO-DPA-BN-BFT and DMA-DPA-BN-BFT) with similar structures were obtained. Intriguingly, DPA-BN-BFT, MeO-DPA-BN-BFT and DMA-DPA-BN-BFT exhibit completely different emission behaviors. Fluorogens DPA-BN-BFT and MeO-DPA-BN-BFT exhibit a typical ACQ effect; in sharp contrast, DMA-DPA-BN-BFT possesses a prominent aggregation induced emission (AIE) effect. To the best of our knowledge, this is the first report to integrate ACQ and AIE properties into one BN aromatic backbone with subtle modified structures. Comprehensive analysis of the crystal structure and theoretical calculations reveal that relatively large twisting angles, multiple intermolecular interactions and tight crystal packing modes endow DMA-DPA-BN-BFT with strong AIE behavior. More importantly, cell imaging demonstrated that luminescent materials DPA-BN-BFT and DMA-DPA-BN-BFT can highly selectively and sensitively detect lipid droplets (LDs) in living MCF-7 cells. Overall, this work provides a new viewpoint of the rational design and synthesis of advanced BN–polycyclic aromatics with AIE features and triggers the discovery of new functions and properties of azaborine chemistry.

A one-stone-two-birds strategy including simultaneous exploration of reactivity and tuning of the optical and electronic properties for BN-fused polycyclic aromatics through flexible regioselective functionalization engineering is presented.     

Annulative π-Extension by Rhodium(III)-Catalyzed Ketone-Directed C−H Activation: Rapid Access to Pyrenes and Related Polycyclic Aromatic Hydrocarbons (PAHs)

Annulative π-extension (APEX) reaction has become a powerful tool for the precise synthesis of well-defined polycyclic aromatic hydrocarbons (PAHs) such as nanographene, graphene, and other PAHs possessing unique structure. Herein, an APEX reaction has been realized at the masked bay-region for the efficient and rapid synthesis of valuable PAH, pyrene, bearing substitutions at the most challenging K-region. Rh^III-catalyzed ketone-directed C−H activation at the peri-position of a naphthyl-derived ketone, alkyne-insertion, intramolecular nucleophilic attack at the carbonyl-group, dehydration, and aromatization steps occurred in one-pot to effectuate the protocol. Employing this strategy, a two-fold APEX reaction on enantiopure BINOL-derived ketones provided access to axially-chiral bipyrene derivatives. The detailed DFT study to support proposed mechanism, and synthesis of helical PAHs like dipyrenothiophene and dipyrenofuran are other highlights of the present study.     

Asymmetric higher-order [10 + n] cycloadditions of palladium-containing 10π-cycloaddends

We uncovered an asymmetric higher-order [10 + 2] cycloaddition reaction between diverse activated alkenes and a new type of π-allylpalladium complex-containing dipole-type 10π-cycloaddend, which was generated in situ from 2-methylene-1-indanols via a dehydrative insertion and deprotonation strategy under double activation of Pd(0) and phosphoric acid. A similar strategy was applied to an asymmetric higher-order [10 + 8] cycloaddition reaction or [10 + 4] cycloaddition reaction by using a heptafulvene derivative or a cyclic enone, respectively, as the acceptor. A variety of polycyclic frameworks imbedding an indene core were generally furnished in moderate to excellent yields with high levels of enantioselectivity by employing a newly designed chiral phosphoramidite ligand.

A type of π-allylpalladium complex-containing 10π-cycloaddend generated from 2-methylene-1-indanols under double activation of Pd(0) and phosphoric acid undergoes asymmetric higher-order [10 + 2] cycloadditions with diverse activated alkenes.     

Visualizing electron delocalization in contorted polycyclic aromatic hydrocarbons

Electron delocalization in contorted polycyclic aromatic hydrocarbon (PAH) molecules was examined through 3D isotropic magnetic shielding (IMS) contour maps built around the molecules using pseudo-van der Waals surfaces. The resulting maps of electron delocalization provided an intuitive, yet detailed and quantitative evaluation of the aromatic, non aromatic, and antiaromatic character of the local and global conjugated cyclic circuits distributed over the molecules. An attractive pictural feature of the 3D IMS contour maps is that they are reminiscent of the Clar π-sextet model of aromaticity. The difference in delocalization patterns between the two faces of the electron circuits in contorted PAHs was clearly visualized. For π-extended contorted PAHs, some splits of the π system resulted in recognizable patterns typical of smaller PAHs. The differences between the delocalization patterns of diastereomeric chiral PAHs could also be visualized. Mapping IMS on pseudo-van der Waals surfaces around contorted PAHs allowed visualization of their superimposed preferred circuits for electron delocalization and hence their local and global aromaticity patterns.

Electron delocalization in contorted polycyclic aromatic hydrocarbon (PAH) molecules was examined through 3D isotropic magnetic shielding (IMS) contour maps built around the molecules using pseudo-van der Waals surfaces.     

Access to tetracoordinate boron-doped polycyclic aromatic hydrocarbons with delayed fluorescence and aggregation-induced emission under mild conditions

Boron-doped polycyclic aromatic hydrocarbons (PAHs) have attracted ongoing attention in the field of optoelectronic materials due to their unique optical and redox properties. To investigate the effect of tetracoordinate boron in PAHs bearing N-heterocycles (indole and carbazole), a facile approach to four-coordinate boron-doped PAHs was developed, which does not require elevated temperature and pre-synthesized functionalized boron reactants. Five tetracoordinate boron-doped PAHs (NBNN-1–NBNN-5) were synthesized with different functional groups. Two of them (NBNN-1 and NBNN-2) could further undergo oxidative coupling reactions to form fused off-plane tetracoordinate boron-doped PAHs NBNN-1f and NBNN-2f. The investigation of photophysical properties showed that the UV/vis absorption and fluorescence emission are significantly red-shifted compared to those of the three-coordinate boron-doped counterparts. In addition, the emission of NBNN-1–NBNN-3 consisted of prompt fluorescence and delayed fluorescence. The compounds NBNN-1f and NBNN-2f showed aggregation-induced emission.

A series of tetracoordinate boron-doped polycyclic aromatic hydrocarbons have been synthesized under mild conditions, featuring delayed fluorescence and aggregation-induced emission.     

Solvent-Tuned Self-Assembled Nanostructures of Chiral l/d-Phenylalanine Derivatives of Protoporphyrin IX

Protoporphyrin IX is a naturally occurring amphiphilic porphyrin with a rigid hydrophobic nonpolar core and two polar propionic acid substitutions on the porphyrin ring. This molecule can be modified on the hydrophilic group, which can lead to strengthened π–π-stacking and spontaneous self-assembly into novel nanostructures. Herein, we use l- phenylalanine and d-phenylalanine to modify protoporphyrin IX, and use the two derivatives for solvophobic-controlled self-assembly. Both derivatives possess two important features: 1) the aromatic core of the porphyrin for dispersive interactions and 2) a chiral amino acid to maximize the influence of chirality on selfassembly. These derivatives lead to the formation of a variety of nanostructure morphologies, such as spheres, nanofibers, lamellar structures, and thread-like and spherical shells. Solution-based self-assembly was determined by UV/Vis, fluorescence, and circular dichroism spectroscopy, and the formed nanostructures were characterized by scanning electron microscopy (SEM). Such engineered porphyrin derivatives could have potential applications in energy transport and storage, supramolecular chemistry, materials science, and medicine.     

Diels-Alder cycloadditions of functionalized (Z)-1-benzylidene-2-methylene cyclohexanes: the beneficial effect of high pressure

Diels-Alder cycloaddition reactions have been studied on substituted (Z)-1-benzylidene-2-methylene cyclohexanes 3. The use of very reactive dienophiles allowed the formation of the expected polycyclic structures whereas hyperbaric conditions (16 kbar) were necessary to form the adducts with less reactive dienophiles. An exo stereoselectivity was observed during the reaction with acrylates.     

Star-shaped and linear nanosized molecules functionalized with hexa-peri-hexabenzocoronene: synthesis and optical properties

[structure: see text] A synthetic strategy promising the establishment of a new star-shaped and linear polycyclic aromatic hydrocarbons (PAHs) family with distinct molecular topologies has been developed. The Sonogashira reaction between the iodide derivatives 2a-e and phenylacetylene catalyzed with Pd(0) affords 3a-e in high yields. The Diels-Alder and decarbonylation reactions between 3a-e and tetraphenylcyclophentadiene following the oxidation by FeCl(3) produce the star-shaped and linear PAHs 5a-e containing a five-membered ring. The structural analysis and the optical properties of all new compounds are performed by a combination of MALDI-TOF mass spectrometry, UV-vis, and fluorescence spectrometry. The electronic and photophysical properties are studied by orthogonal comparisons of the absorption and fluorescence spectra in THF solutions, which not only give insight into the interactions among aromatic submoieties in each molecule and the effects of meta-conjugation and para-conjugation on electronic delocalization, but also indicate effective conjugation length variations from oligophenylacetylenes 3a-e to oligophenylene dendrimers 4a-e and PAHs 5a-e. The star-shaped 5c exhibits the highest aggregation in excited states compared with the other four hexa-peri-hexabenzocoronene (HBC) derivatives.     

Fast Atom Bombardment Combined with Mass Spectrometry or Characterization of Polycyclic Aromatic Hydrocarbons

A new approach using fast atom bombardment combined with mass spectrometry to characterize polycyclic aromatic hydrocarbons (PAHs) in the range of 128–252 u molecular weight is described. Sulfolane was employed as a liquid matrix for these π-conjugated hydrocarbons. Bombardment of sulfolane solution of certain PAHs with an atom beam produces both radical cation (M⁺) and protonated molecule [(M + H)⁺], with no evidence of fragmentation. Collisional activation of the fast atom bombardment-desorbed M⁺ ions, however, results in several structure-specific fragment ions. Structural differences in a few isomeric hydrocarbons can be detected using the [(M + H)⁺]/[M⁺] abundance ratio and in the pyrene-fluoranthene pair by the B/E linked-field-collision-activated dissociation data. The [(M + H)⁺]/[M⁺] was found to be compound-specific and correlated well with certain properties (resonance energy, proton affinity, and ionizing energy) of PAHs.     

Enrichment of polycyclic aromatic hydrocarbons in seawater with magnesium oxide microspheres as a solid-phase extraction sorbent

The enrichment of polycyclic aromatic hydrocarbons (PAHs) in water samples with magnesium oxide (MgO) microspheres was evaluated, and four 3-5-ring PAHs were used as probes to validate the adsorption capacity of the material. Factors affecting the recovery of PAHs were investigated in detail, including the type and concentration of organic modifiers, elution solvents, particle size of the adsorbent, volume and flow rate of the samples, and the lifetime of MgO cartridges. The recoveries of four PAHs extracted from 20 mL of seawater spiked with standard PAHs ranged from 85.8% to 102.0% under the optimised conditions. The limits of detection varied from 1.83 ng L⁻¹ to 16.03 ng L⁻¹, indicating that the analytical method was highly sensitive. Additionally, the proposed method was successfully used to enrich PAHs in seawater. Compared to conventional methods, the proposed method consumed less organic modifier (5% acetone), and cheaper sorbents with comparable extraction efficiency were employed.     

“Broken-hearted” carbon bowl via electron shuttle reaction: energetics and electron coupling

Unprecedented one-step C C bond cleavage leading to opening of the buckybowl (π-bowl), that could provide access to carbon-rich structures with previously inaccessible topologies, is reported; highlighting the possibility to implement drastically different synthetic routes to π-bowls in contrast to conventional ones applied for polycyclic aromatic hydrocarbons. Through theoretical modeling, we evaluated the mechanistic pathways feasible for π-bowl planarization and factors that could affect such a transformation including strain and released energies. Through employment of Marcus theory, optical spectroscopy, and crystallographic analysis, we estimated the possibility of charge transfer and electron coupling between “open” corannulene and a strong electron acceptor such as 7,7,8,8-tetracyanoquinodimethane. Alternative to a one-pot solid-state corannulene “unzipping” route, we reported a nine-step solution-based approach for preparation of novel planar “open” corannulene-based derivatives in which electronic structures and photophysical profiles were estimated through the energies and isosurfaces of the frontier natural transition orbitals.

An electron shuttle contributed to breaking corannulene''s heart through a unique one-step reductive C C bond cleavage in the traditionally robust π-bowl. The heartbreak did not stop there as “broken analogs” were developed through a solution-phase route.     

Functionalization of Pentacene: A Facile and Versatile Approach to Contorted Polycyclic Aromatic Hydrocarbons

In this work, a facile and versatile strategy for the synthesis of contorted polycyclic aromatic hydrocarbons (PAHs) starting from the functionalized pentacene was established. A series of novel PAHs 1 – 4 and their derivatives were synthesized through a simple two-step synthesis procedure involving an intramolecular reductive Friedel–Crafts cyclization of four newly synthesized pentacene aldehydes 5 – 8 as a key step. All the molecules were confirmed by single-crystal X-ray diffraction and their photophysical and electrochemical properties were studied in detail. Interestingly, the most striking feature of 1 – 4 is their highly contorted carbon structures and the accompanying helical chirality. In particular, the optical resolution of 2 was successfully achieved by chiral-phase HPLC, and the enantiomers were characterized by circular dichroism and circularly polarized luminescence spectroscopy. Despite the highly nonplanar conformations, these contorted PAHs exhibited emissive properties with moderate-to-good fluorescence quantum yields, implying the potential utility of this series PAHs as high-quality organic laser dyes. By using a self-assembly method with the help of epoxy resin, a bottle microlaser based on 3 a was successfully illustrated with a lasing wavelength of 567.8 nm at a threshold of 0.3 mJ/cm². We believe that this work will shed light on the chemical versatility of pentacene and its derivatives in the construction of novel functionalized PAHs.     

A divergent route to core- and peripherally functionalized diazacoronenes that act as colorimetric and fluorescence proton sensors

Combining core annulation and peripheral group modification, we have demonstrated a divergent synthesis of a family of highly functionalized coronene derivatives from a readily accessible dichlorodiazaperylene intermediate. Various reactions, such as aromatic nucleophilic substitution, Kumada coupling and Suzuki coupling proceed effectively on α-positions of the pyridine sites, giving rise to alkoxy, thioalkyl, alkyl or aryl substituted polycyclic aromatic hydrocarbons. In addition to peripheral group modulation, the aromatic core structures can be altered by annulation with thiophene or benzene ring systems. Corresponding single crystal X-ray diffraction and optical studies indicate that the heteroatom linkages not only impact the solid state packing, but also significantly influence the optoelectronic properties. Moreover, these azacoronene derivatives display significant acid-induced spectroscopic changes, suggesting their great potential as colorimetric and fluorescence proton sensors.     

[4+2] Cycloaddition on densely functionalized cyclopentadiene

The Diels-Alder (DA) and hetero-Diels-Alder (HDA) reaction of N-(2,4-dicyano-1,5-dimethyl-3-phenylcyclopenta-2,4-dienyl)-2,2,2-trifluoroacetamide 1 can be conveniently used for the synthesis of biarylic and polycyclic compounds, depending on whether you use alkynes or alkenes as dienophiles. We observe a totally regioselectivity and endo-diastereoselectivity of the cycloaddition reactions.