Electrochemically controlled rectification in symmetric single-molecule junctions.

Single-molecule electrochemical science has advanced over the past decades and now extends well beyond molecular imaging, to molecular electronics functions such as rectification and amplification. Rectification is conceptually the simplest but has involved mostly challenging chemical synthesis of asymmetric molecular structures or asymmetric materials and geometry of the two enclosing electrodes. Here we propose an experimental and theoretical strategy for building and tuning in situ (in operando) rectification in two symmetric molecular structures in electrochemical environment. The molecules were designed to conduct electronically via either their lowest unoccupied molecular orbital (LUMO; electron transfer) or highest occupied molecular orbital (HOMO; "hole transfer"). We used a bipotentiostat to control separately the electrochemical potential of the tip and substrate electrodes of an electrochemical scanning tunneling microscope (EC-STM), which leads to independent energy alignment of the STM tip, the molecule, and the STM substrate. By creating an asymmetric energy alignment, we observed single-molecule rectification of each molecule within a voltage range of ±0.5 V. By varying both the dominating charge transporting LUMO or HOMO energy and the electrolyte concentration, we achieved tuning of the polarity as well as the amplitude of the rectification. We have extended an earlier proposed theory that predicts electrolyte-controlled rectification to rationalize all the observed in situ rectification features and found excellent agreement between theory and experiments. Our study thus offers a way toward building controllable single-molecule rectifying devices without involving asymmetric molecular structures.

Nonalternant Nanographenes Containing N-Centered Cyclopenta[ef]heptalene and Aza[7]Helicene Units.

Introducing helical subunits into negatively curved π-systems has a significant effect on both the molecular geometry and photophysical properties; however, the synthesis of these helical π-systems embedded with nonbenzenoid subunits remains challenging due to the high strain deriving from both the curvature and helix. Here, we report a family of nonalternant nanographenes containing a nitrogen (N)-doped cyclopenta[ef]heptalene unit. Among them, CPH-2 and CPH-3 can be viewed as hybrids of benzoannulated cyclopenta[ef]heptalene and aza[7]helicene. The crystal structures revealed a saddle geometry for CPH-1, a saddle-helix hybrid for CPH-2, and a twist-helix hybrid for CPH-3. Experimental measurements and theoretical calculations indicate that the saddle moieties in CPHs undergo flexible conformational changes at room temperature, while the aza[7]helicene subunit exhibits a dramatically increased racemization energy barrier (78.2 kcal mol-1 for CPH-2, 143.2 kcal mol-1 for CPH-3). The combination of the nitrogen lone electron pairs of the N-doped cyclopenta[ef]heptalene unit with the twisted helix fragments results in rich photophysics with distinctive fluorescence and phosphorescence in CPH-1 and CPH-2 and the similar energy fluorescence and phosphorescence in CPH-3. Both enantiopure CPH-2 and CPH-3 display distinct circular dichroism (CD) signals in the UV-vis range. Notably, compared to the reported fully π-extended helical nanographenes, CPH-3 exhibits excellent chiroptical properties with a |gabs| value of 1.0 × 10-2 and a |glum| value of 7.0 × 10-3; these values are among the highest for helical nanographenes.

Highly Selective On-Surface Ring-Opening of Aromatic Azulene Moiety.

Controllable ring-opening of polycyclic aromatic hydrocarbons plays a crucial role in various chemical and biological processes. However, breaking down aromatic covalent C-C bonds is exceptionally challenging due to their high stability and strong aromaticity. This study presents a seminal report on the precise and highly selective on-surface ring-opening of the seven-membered ring within the aromatic azulene moieties under mild conditions. The chemical structures of the resulting products were identified using bond-resolved scanning probe microscopy. Furthermore, through density functional theory calculations, we uncovered the mechanism behind the ring-opening process and elucidated its chemical driving force. The key to achieving this ring-opening process lies in manipulating the local aromaticity of the aromatic azulene moiety through strain-induced internal ring rearrangement and cyclodehydrogenation. By precisely controlling these factors, we successfully triggered the desired ring-opening reaction. Our findings not only provide valuable insights into the ring-opening process of polycyclic aromatic hydrocarbons but also open up new possibilities for the manipulation and reconstruction of these important chemical structures.

Exceptionally clean single-electron transistors from solutions of molecular graphene nanoribbons.

Only single-electron transistors with a certain level of cleanliness, where all states can be properly accessed, can be used for quantum experiments. To reveal their exceptional properties, carbon nanomaterials need to be stripped down to a single element: graphene has been exfoliated into a single sheet, and carbon nanotubes can reveal their vibrational, spin and quantum coherence properties only after being suspended across trenches1-3. Molecular graphene nanoribbons4-6 now provide carbon nanostructures with single-atom precision but suffer from poor solubility, similar to carbon nanotubes. Here we demonstrate the massive enhancement of the solubility of graphene nanoribbons by edge functionalization, to yield ultra-clean transport devices with sharp single-electron features. Strong electron-vibron coupling leads to a prominent Franck-Condon blockade, and the atomic definition of the edges allows identifying the associated transverse bending mode. These results demonstrate how molecular graphene can yield exceptionally clean electronic devices directly from solution. The sharpness of the electronic features opens a path to the exploitation of spin and vibrational properties in atomically precise graphene nanostructures.

Helical Nanographenes Bearing Pentagon-Heptagon Pairs by Stepwise Dehydrocyclization.

The incorporation of pentagon-heptagon pairs into helical nanographenes lacks a facile synthetic route, and the impact of these pairs on chiroptical properties remains unclear. In this study, a method for the stepwise construction of pentagon-heptagon pairs in helical nanographenes by the dehydrogenation of [6]helicene units was developed. Three helical nanographenes containing pentagon-heptagon pairs were synthesized and characterized using this approach. A wide variation in the molecular geometries and photophysical properties of these helical nanographenes was observed, with changes in the helical length of these structures and the introduction of the pentagon-heptagon pairs. The embedded pentagon-heptagon pairs reduced the oxidation potential of the synthesized helical nanographenes. The high isomerization energy barriers enabled the chiral resolution of the helicene enantiomers. Chiroptical investigations revealed remarkably enhanced circularly polarized luminescence and luminescence dissymmetry factors with an increasing number of the pentagon-heptagon pairs.

BN-Embedded Cycloarenes: One-Pot Borylation Synthesis, Photoelectric Properties, and Application in Perovskite Solar Cells.

Incorporating heteroatoms, such as nitrogen, oxygen, and/or sulfur atoms, into cycloarenes can effectively regulate their molecular geometries and (opto)electronic properties. However, the rarity of cycloarenes and heterocycloarenes limits the further exploitation of their applications. Herein, we designed and synthesized the first examples of boron and nitrogen (BN)-doped cycloarenes (BN-C1 and BN-C2) via one-pot intramolecular electrophilic borylation of imine-based macrocycles. BN-C2 adopts a bowl-shaped conformation, while BN-C1 possesses a planar geometry. Accordingly, the solubility of BN-C2 was significantly improved by replacing two hexagons in BN-C1 with two N-pentagons, due to the creation of distortions away from planarity. Various experiments and theoretical calculations were carried out for heterocycloarenes BN-C1 and BN-C2, demonstrating that the incorporated BN bonds diminish the aromaticity of 1,2-azaborine units and their adjacent benzenoid rings but preserve the dominant aromatic properties of pristine kekulene. Importantly, when two additional electron-rich nitrogen atoms were introduced, the highest occupied molecular orbital energy level of BN-C2 was elaborately lifted compared with that of BN-C1. As a result, the energy-level alignment of BN-C2 with the work function of the anode and the perovskite layer was suitable. Therefore, for the first time, heterocycloarene (BN-C2) was explored as a hole-transporting layer in inverted perovskite solar cell devices, in which the power conversion efficiency reached 14.4%.

Two-Step Synthesis of B2 N2 -Doped Polycyclic Aromatic Hydrocarbon Containing Pentagonal and Heptagonal Rings with Long-Lived Delayed Fluorescence.

Pentagon-heptagon embedded polycyclic aromatic hydrocarbons (PAHs) have aroused increasing attention in recent years due to their unique physicochemical properties. Here, for the first time, this report demonstrates a facile method for the synthesis of a novel B2 N2 -doped PAH (BN-2) containing two pairs of pentagonal and heptagonal rings in only two steps. In the solid state of BN-2, two different conformations, including saddle-shaped and up-down geometries, are observed. Through a combined spectroscopic and calculation study, the excited-state dynamics of BN-2 is well-investigated in this current work. The resultant pentagon-heptagon embedded B2 N2 -doped BN-2 displays both prompt fluorescence and long-lived delayed fluorescence components at room temperature, with the triplet excited-state lifetime in the microsecond time region (τ = 19 µs). The triplet-triplet annihilation is assigned as the mechanism for the observed long-lived delayed fluorescence. Computational analyses attributed this observation to the small energy separation between the singlet and triplet excited states, facilitating the intersystem crossing (ISC) process which is further validated by the ultrafast spectroscopic measurements.

SLC25A32 promotes malignant progression of glioblastoma by activating PI3K-AKT signaling pathway.

BACKGROUND: Solute carrier family 25 member 32 (SLC25A32) is an important member of SLC25A family and plays a role in folate transport metabolism. However, the mechanism and function of SLC25A32 in the progression of human glioblastoma (GBM) remain unclear. METHODS: In this study, folate related gene analysis was performed to explore gene expression profiles in low-grade glioma (LGG) and GBM. Western blotting, real-time quantitative PCR (qRT-PCR), and immunohistochemistry (IHC) were used to confirm the expression levels of SLC25A32 in GBM tissues and cell lines. CCK-8 assays, colony formation assays, and Edu assays were performed to assess the role of SLC25A32 on proliferation in GBM in vitro. A 3D sphere invasion assay and an ex vivo co-culture invasion model were performed to assess the effects of SLC25A32 on invasion in GBM. RESULTS: Elevated expression of SLC25A32 was observed in GBM, and high SLC25A32 expression was associated with a high glioma grade and poorer prognosis. Immunohistochemistry performed with anti-SLC25A32 on samples from an independent cohort of patients confirmed these results. Knockdown of SLC25A32 inhibited the proliferation and invasion of GBM cells, but overexpression of SLC25A32 significantly promoted cell growth and invasion. These effects were mainly due to the activation of the PI3K-AKT-mTOR signaling pathway. CONCLUSION: Our study demonstrated that SLC25A32 plays a significant role in promoting the malignant phenotype of GBM. Therefore, SLC25A32 can be used as an independent prognostic factor in patients with GBM, providing a new target for the comprehensive treatment of GBM.

Fully neuroendoscopic resection of cerebellopontine angle tumors through a retrosigmoid approach: a retrospective single-center study.

The objective of this study is to preliminarily investigate the surgical safety, efficacy, techniques, and clinical value of fully neuroendoscopic surgery for the resection of cerebellopontine angle (CPA) tumors via a retrosigmoid approach. The clinical data of 47 cerebellopontine angle area (CPA) tumors that were treated by full neuroendoscopic surgery from June 2014 to June 2023 were retrospectively analyzed. The efficacy and advantages of the surgical techniques were evaluated based on indicators such as duration of the surgery, neuroendoscopic techniques, intraoperative integrity of nerves and blood vessels, extent of tumor resection, outcomes or postoperative symptoms, and incidence of complications. The 47 cases of cerebellopontine angle tumors include 34 cases of epidermoid cysts, 7 cases of vestibular schwannomas, and 6 cases of meningiomas. All patients underwent fully neuroendoscopic surgery. Twenty tumors were removed using the one-surgeon two-hands technique, and 27 tumors were removed using the two-surgeons four-hands technique. The anatomical integrity of the affected cranial nerves was preserved in all 47 cases. None of the patients suffered a postoperative hemorrhage, cerebrospinal fluid leak, and aseptic or septic meningitis, or died. The rate of total tumor resection was 72.3% (34/47), and the symptom improvement rate was 89.4% (42/47). All patients were followed up for 2 to 12 months, and none died nor showed any signs of tumor recurrence. By analyzing 47 fully neuroendoscopic resections of CPA tumors using the posterior sigmoid sinus approach in our center, we believe that such method allows complete, safe, and effective resection of CPA tumors and is thereby worthy of clinical promotion.

Facile Synthesis of Nitrogen-Doped Nanographenes with Joined Nonhexagons via a Ring Expansion Strategy.

Synthetic methodology is considered a holy grail in both organic chemistry and materials science. Over the past few decades, researchers have explored graphene-type molecules (or nanographenes) through classic Scholl oxidative cyclodehydrogenation. Despite the successes achieved with various nanographenes, the development of new methods to synthesize these highly desired molecules lags behind. Herein, we developed a facile and effective method to produce a series of nanographenes bearing nitrogen (N)-doped pentagon-heptagon pairs in acceptable yields. Modification of the heptagonal ring endowed the resultant nanographenes with tunable physicochemical properties; for instance, M9 exhibited both aggregation-caused quenching and aggregation-induced emission behavior. Most strikingly, novel nanographenes containing N-doped pentagon-octagon pairs were also obtained using the same synthetic strategy, demonstrating the superior versatility and efficiency of the proposed ring expansion method.

Extension of Non-alternant Nanographenes Containing Nitrogen-Doped Stone-Thrower-Wales Defects.

Non-alternant topologies have attracted considerable attention due to their unique physiochemical characteristics in recent years. Here, three novel topological nanographenes molecular models of nitrogen-doped Stone-Thrower-Wales (S-T-W) defects were achieved through intramolecular direct arylation. Their chemical structures were unambiguously elucidated by single-crystal analysis. Among them, threefold intramolecular direct arylation compound (C42 H21 N) is the largest nanographene bearing a N-doped non-alternant topology to date, in which the non-benzenoid rings account for 83 % of the total molecular skeleton. The absorption maxima of this compound was located in the near-infrared region with a long tail up to 900 nm, which was much longer than those reported for similarly sized N-doped nanographene with six-membered rings (C40 H15 N). In addition, the electronic energy gaps of these series compounds clearly decreased with the introduction of non-alternant topologies (from 2.27 eV to 1.50 eV). It is noteworthy that C42 H21 N possesses such a low energy gap (Eg opt =1.40 eV; Eg cv =1.50 eV), yet is highly stable under ambient conditions. Our work reported herein demonstrates that the non-alternant topology could significantly influence the electronic configurations of nanocarbons, where the introduction of a non-alternanting topology may be an effective way to narrow the energy gap without extending the molecular π-conjugation.

Synthesis of a Dicyclohepta[a,g]heptalene-Containing Polycyclic Conjugated Hydrocarbon and the Impact of Non-Alternant Topologies.

Incorporating non-hexagonal rings into polycyclic conjugated hydrocarbons (PCHs) can significantly affect their electronic and optoelectronic properties and chemical reactivities. Here, we report the first bottom-up synthesis of a dicyclohepta[a,g]heptalene-embedded PCH (1) with four continuous heptagons, which are arranged in a "Z" shape. Compared with its structural isomer bischrysene 1 R with only hexagonal rings, compound 1 presents a distinct antiaromatic character, especially the inner heptalene core, which possesses clear antiaromatic nature. In addition, PCH 1 exhibits a narrower highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap than its benzenoid contrast 1 R, as verified by experimental measurements and theoretical calculations. Our work reported herein not only provides a new way to synthesize novel PCHs with non-alternant topologies but also offers the possibility to tune their electronic and optical properties.

A BN-Doped U-Shaped Heteroacene as a Molecular Floating Gate for Ambipolar Charge Trapping Memory.

Two wide-band gap U-shaped polycyclic aromatic hydrocarbons with/without boron and nitrogen (BN-) doping (BN-1 and C-1) were synthesized to tune the electronic features to suit the performance requirements for organic field-effect transistor memory (OFET-NVM). The chemical structures were characterized by scanning tunneling microscopy and single-crystal diffraction. Owing to the electron-donor effect of N and the high electron affinity of B, the BN-1-based OFET-NVM displays large ambipolar memory windows and an enhanced charge storage density compared to C-1 and most reported small molecules. A novel supramolecular system formed from BN-1 and PMMA contributes to fabricating uniform films with homogeneous microstructures, which serve as a two-in-one tunnelling dielectric and charge-trapping layer to realize long-term charge retention and reliable endurance. Our results demonstrate that both BN doping and supramolecular engineering are crucial for the charge trapping of OFET-NVM.

Cove-Edged Graphene Nanoribbons with Incorporation of Periodic Zigzag-Edge Segments.

Structurally precision graphene nanoribbons (GNRs) are promising candidates for next-generation nanoelectronics due to their intriguing and tunable electronic structures. GNRs with hybrid edge structures often confer them unique geometries associated with exotic physicochemical properties. Herein, a novel type of cove-edged GNRs with periodic short zigzag-edge segments is demonstrated. The bandgap of this GNR family can be tuned using an interplay between the length of the zigzag segments and the distance of two adjacent cove units along the opposite edges, which can be converted from semiconducting to nearly metallic. A family member with periodic cove-zigzag edges based on N = 6 zigzag-edged GNR, namely 6-CZGNR-(2,1), is successfully synthesized in solution through the Scholl reaction of a unique snakelike polymer precursor (10) that is achieved by the Yamamoto coupling of a structurally flexible S-shaped phenanthrene-based monomer (1). The efficiency of cyclodehydrogenation of polymer 10 toward 6-CZGNR-(2,1) is validated by FT-IR, Raman, and UV-vis spectroscopies, as well as by the study of two representative model compounds (2 and 3). Remarkably, the resultant 6-CZGNR-(2,1) exhibits an extended and broad absorption in the near-infrared region with a record narrow optical bandgap of 0.99 eV among the reported solution-synthesized GNRs. Moreover, 6-CZGNR-(2,1) exhibits a high macroscopic carrier mobility of ∼20 cm2 V-1 s-1 determined by terahertz spectroscopy, primarily due to the intrinsically small effective mass (m*e = m*h = 0.17 m0), rendering this GNR a promising candidate for nanoelectronics.

Benzo-Extended Cyclohepta[def]fluorene Derivatives with Very Low-Lying Triplet States.

Open-shell non-alternant polycyclic hydrocarbons (PHs) are attracting increasing attention due to their promising applications in organic spintronics and quantum computing. Herein we report the synthesis of three cyclohepta[def]fluorene-based diradicaloids (1-3), by fusion of benzo rings on its periphery for the thermodynamic stabilization, as evidenced by multiple characterization techniques. Remarkably, all of them display a very narrow optical energy gap (Eg opt =0.52-0.69 eV) and persistent stability under ambient conditions (t1/2 =11.7-33.3 h). More importantly, this new type of diradicaloids possess a low-lying triplet state with an extremely small singlet-triplet energy gap, as low as 0.002 kcal mol-1 , with a clear dependence on the molecular size. This family of compounds thus offers a new route to create non-alternant open-shell PHs with high-spin ground states, and opens up novel possibilities and insights into understanding the structure-property relationships.

Defective Nanographenes Containing Seven-Five-Seven (7-5-7)-Membered Rings.

Defects have been observed in graphene and are expected to play a key role in its optical, electronic, and magnetic properties. However, because most of the studies focused on the structural characterization, the implications of topological defects on the physicochemical properties of graphene remain poorly understood. Here, we demonstrate a bottom-up synthesis of three novel nanographenes (1-3) with well-defined defects in which seven-five-seven (7-5-7)-membered rings were introduced to their sp2 carbon frameworks. From the X-ray crystallographic analysis, compound 1 adopts a nearly planar structure. Compound 2, with an additional five-membered ring compared to 1, possesses a slightly saddle-shaped geometry. Compound 3, which can be regarded as the "head-to-head" fusion of 1 with two bonds, features two saddles connected together. The resultant defective nanographenes 1-3 were well-investigated by UV-vis absorption, cyclic voltammetry, and time-resolved absorption spectra and further corroborated by density functional theory (DFT) calculations. Detailed experimental and theoretical investigations elucidate that these three nanographenes 1-3 exhibit an anti-aromatic character in their ground states and display a high stability under ambient conditions, which contrast with the reported unstable biradicaloid nanographenes that contain heptagons. Our work reported herein offers insights into the understanding of structure-related properties and enables the control of the electronic structures of expanded nanographenes with atomically precise defects.

Acute effects of CH3NH3PbI3 perovskite on Scenedesmus obliquus and Daphnia magana in aquatic environment.

CH3NH3PbI3 is one of the most widely studied and most promising photoelectric conversion materials for large-scale application. However, once it is discharged into the aquatic environment, it will release a variety of lethal substances to the aquatic organisms. Herein, two typical aquatic pollution indicators, Scenedesmus obliquus (a typical phytoplankton) and Daphnia magna (a typical zooplankton), were used to assess the acute effects of CH3NH3PbI3 perovskite on aquatic organisms. The results showed that, when the initial CH3NH3PbI3 perovskite level (CPL) was 40 mg L-1 or higher, the growth of S. obliquus would be remarkably inhibited with significant decreases of chlorophyll content and protein content. And when the CPL was over 5 mg L-1, the survival of D. magna would be notably threatened. Specifically, the 72 h EC-50 of CH3NH3PbI3 perovskite to S. obliquus was calculated as 37.21 mg L-1, and the 24 h LC-50 of this perovskite to D. magna adults and neonates were calculated as 37.53 mg L-1 and 18.55 mg L-1, respectively. Moreover, remarkably solution pH declination and large amounts of lead bio-accumulation was observed in the both acute experiments, which could be the main reasons causing the above acute effects. Considering the strong acute effects of these CH3NH3PbI3 perovskite materials and their attractive application prospect, more attentions should be paid on their harmness to the environment.

A Molecular Transformer: A π-Conjugated Macrocycle as an Adaptable Host.

Here, we report a facile method to synthesize a series of macrocycles with different conformations. The planar macrocycle dimer (1), twisted macrocycle trimer (2) and "figure-eight" tetramer (3) are clearly elucidated by X-ray single-crystal analysis, in which the electron-rich phenanthrene units offer the possibility of supramolecular assembly. As expected, in the solid state, 1 and 3 assemble into a columnar stack and an interlocking dimer, respectively, via π-π interactions between the phenanthrene units. Compared to the rigid conformation of dimer 1, the structure of tetramer 3 is more flexible due to its enlarged ring size. 3 can deform from a figure-eight into a boat-shaped geometry to host a planar electron-deficient guest using its electron-rich phenanthrene units. When assembled with spherical electron-deficient C60 , interestingly, 3 further undergoes a conformational transformation from a figure-eight to a belt shape in order to host C60 . These supramolecular assembly behaviors of 3 demonstrate that it is an adaptable macrocyclic host for both planar molecules and fullerenes.

A Modular Cascade Synthetic Strategy Toward Structurally Constrained Boron-Doped Polycyclic Aromatic Hydrocarbons.

A novel synthetic strategy was developed for the construction of difficult-to-access structurally constrained boron-doped polycyclic aromatic hydrocarbons (sc-B-PAHs) via a cascade reaction from the readily available ortho-aryl-substituted diarylalkynes. This domino process involves borylative cyclization, 1,4-boron migration and successive two-fold electrophilic borylation. Two types of sc-B-PAHs bearing B-doped [4]helicene (1 a-1 i) or BN-doped [4]helicene (1 n-1 t) and double [4]helicene (1 u-1 v) are constructed by this cascade reaction. Remarkably, this synthetic strategy is characterized by modest yields (20-50 %) and broad substrate scope (18 examples) with versatile functional group tolerance. The resultant sc-B-PAHs show good stability under ambient conditions and are thoroughly investigated by X-ray crystallography, UV/Vis absorption and fluorescence spectroscopy, and cyclic voltammetry. Interestingly enough, BN-doped [4]helicene 1 o forms a unique alternating π-stacked dimer of enantiomers within a helical columnar superstructure, while BN-doped double [4]helicene 1 u establishes an unprecedented π-stacked trimeric sandwich structure with a rare 2D lamellar π-stacking. The synthetic approach reported herein represents a powerful tool for the rapid generation of novel sc-B-PAHs, which are highly attractive for the elucidation of the structure-property relationship and for potential optoelectronic applications.

Persistent peri-Heptacene: Synthesis and In Situ Characterization.

n-peri-Acenes (n-PAs) have gained interest as model systems of zigzag-edged graphene nanoribbons for potential applications in nanoelectronics and spintronics. However, the synthesis of n-PAs larger than peri-tetracene remains challenging because of their intrinsic open-shell character and high reactivity. Presented here is the synthesis of a hitherto unknown n-PA, that is, peri-heptacene (7-PA), in which the reactive zigzag edges are kinetically protected with eight 4-tBu-C6 H4 groups. The formation of 7-PA is validated by high-resolution mass spectrometry and in situ FT-Raman spectroscopy. 7-PA displays a narrow optical energy gap of 1.01 eV and exhibits persistent stability (t1/2 ≈25 min) under inert conditions. Moreover, electron-spin resonance measurements and theoretical studies reveal that 7-PA exhibits an open-shell feature and a significant tetraradical character. This strategy could be considered a modular approach for the construction of next-generation (3 N+1)-PAs (where N≥3).