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Non‐benzenoid diradicaloids possessing high‐spin ground states are attractive synthetic targets given their high potential for spintronics and quantum computing. Nevertheless, the synthesis of such compounds remains highly challenging due to their inherent instability. In this work, we present the synthetic attempt towards creating a non‐benzenoid diradicaloid (1) with a triplet ground state by fusing two cyclohepta[def]fluorene units onto a benzene ring. Our synthetic approach involves both oxidation and reduction pathways. In the oxidation path, we obtained the partially dehydrogenated products 1+H and 1+2H containing an indeno[1,2‐b]fluorene core from the tetrahydro precursor (2). However, further dehydrogenation to afford the target molecule (1) did not proceed. On the other hand, with the reduction pathway, a novel tetraketone precursor (9) with two pairs of pentagons and heptagons was successfully synthesized. The subsequent nucleophilic attack however was proved to be difficult probably due to the unselective nucleophilic addition on the zigzag nanographene ketones. Furthermore, UV‐vis absorption, cyclic voltammetry, and theoretical calculations were conducted to explore the optical, electrochemical properties, and aromaticity of all the obtained molecules (1+H, 1+2H and 9). Although the desired target 1 is not achieved, our work provides insight into designing novel high‐spin non‐benzenoid NGs based on nonalternant cyclohepta[def]fluorene system. [ABSTRACT FROM AUTHOR]

Xiaolangdi Reservoir is a key control project to control the water and sediment in the lower Yellow River, and a timely and accurate grasp of the reservoir’s water storage status is essential for the function of the reservoir. This study used all available Landsat images (789 scenes) and adopted the modified normalized difference water index, enhanced vegetation index, and normalized difference vegetation index to map the surface water from 1999 to 2019 in Google Earth Engine (GEE) cloud platform. The spatiotemporal characteristics of the surface water body area changes in the Xiaolangdi Reservoir in the past 21 years are analyzed from the water body type division, area change, type conversion, and the driving force of the Xiaolangdi water body area changes was analyzed. The results showed that (1) the overall accuracy of the water body extraction method was 98.86%, and the kappa coefficient was 0.96; (2) the maximum water body area of the Xiaolangdi Reservoir varies greatly between inter-annual and intra-annual, and seasonal water body and permanent water body have uneven spatiotemporal distribution; (3) in the conversion of water body types, the increased seasonal water body area of the Xiaolangdi Reservoir from 1999 to 2019 was mainly formed by the conversion of permanent water body, and the reduced permanent water body area was mainly caused by non-water conversion; and (4) the change of the water body area of the Xiaolangdi Reservoir has a weak negative correlation with natural factors such as precipitation and temperature, and population. It is positively correlated with seven indicators such as runoff and regional gross domestic product (GDP). The findings of the research will provide necessary data support for the management and planning of soil and water resources in the Xiaolangdi Reservoir.

In this paper, we proposed a generalized mosquito-borne epidemic model with a general nonlinear incidence rate, which was studied from both deterministic and stochastic insights. In the deterministic model, we proved that the endemic equilibrium was globally asymptotically stable when the basic reproduction number R 0 was greater than unity and the disease free equilibrium was globally asymptotically stable when R 0 was lower than unity. In addition, considering the effect of environmental noise on the spread of infectious diseases, we developed a stochastic model in which the infection rates were assumed to satisfy the mean-reverting log-normal Ornstein-Uhlenbeck process. For this stochastic model, two critical values, known as R 0 s and R 0 E , were introduced to determine whether the disease will persist or die out. Additionally, the exact probability density function of the stationary distribution near the quasi-equilibrium point was obtained. Numerical simulations were conducted to validate the results obtained and to examine the impact of stochastic perturbations on the model. In this paper, we proposed a generalized mosquito-borne epidemic model with a general nonlinear incidence rate, which was studied from both deterministic and stochastic insights. In the deterministic model, we proved that the endemic equilibrium was globally asymptotically stable when the basic reproduction number was greater than unity and the disease free equilibrium was globally asymptotically stable when was lower than unity. In addition, considering the effect of environmental noise on the spread of infectious diseases, we developed a stochastic model in which the infection rates were assumed to satisfy the mean-reverting log-normal Ornstein-Uhlenbeck process. For this stochastic model, two critical values, known as and , were introduced to determine whether the disease will persist or die out. Additionally, the exact probability density function of the stationary distribution near the quasi-equilibrium point was obtained. Numerical simulations were conducted to validate the results obtained and to examine the impact of stochastic perturbations on the model. [ABSTRACT FROM AUTHOR]

Helikale Nanographene (NG) mit hohen Quantenausbeuten und starken chiroptischen Antworten sind entscheidend für die Entwicklung von lumineszenten Materialien mit zirkularer Polarisation (engl. circular polarized luminescence, CPL). Hier berichten wir von der erfolgreichen Synthese neuartiger π‐erweiterter Doppel‐[7]Helicene (ED7Hs), bei denen sich zwei Helicen‐Einheiten meta bzw. para am zentralen Benzenring befinden. Sie sind damit strukturelle Isomere des bekannten ortho‐ED7H. Die strukturelle Integrität und Geometrie der ED7Hs wurde eindeutig durch Röntgen‐Einkristalldiffraktometrie aufgeklärt. Die ED7Hs besitzen eine ausgeprägte Fluoreszenz mit Quantenausbeuten über 40 %. Durch Variation der relativen Positionen der Doppel‐[7]Helicene am zentralen Benzenring (ortho, meta, para) kann eine außergewöhnliche Verstärkung der chiroptischen Eigenschaften registriert werden. Diese Verbesserung zeigt sich in einem etwa fünffachen Anstieg der Absorbanz und Lumineszenz‐Dissymmetriefaktoren (gabs und glum) sowie einer erhöhten CPL‐Helligkeit von bis zu 176 M−1 cm−1, was die Leistung der meisten helicenbasierten chiralen NGs übertrifft. Des weiteren zeigen DFT‐Simulationen, dass die relative geometrische Lage der [7]Helicene eine präzise Anpassung der elektrischen und magnetischen Übergangsdipolmomente zur Folge hat, welche die beobachteten Verstärkungen der chiroptischen Eigenschaften erklären. Diese Studie liefert eine effektive Strategie zur Verstärkung der CPL‐Eigenschaften chiraler Nanographene, welche ihre Anwendbarkeit als CPL‐Emitter verbessert. [ABSTRACT FROM AUTHOR]

Carbon nanomaterials are expected to be bright and efficient emitters, but structural disorder, intermolecular interactions and the intrinsic presence of dark states suppress their photoluminescence. Here, we study synthetically-made graphene nanoribbons with atomically precise edges and which are designed to suppress intermolecular interactions to demonstrate strong photoluminescence in both solutions and thin films. The resulting high spectral resolution reveals strong vibron-electron coupling from the radial-breathing-like mode of the ribbons. In addition, their cove-edge structure produces inter-valley mixing, which brightens conventionally-dark states to generate hitherto-unrecognised twilight states as predicted by theory. The coupling of these states to the nanoribbon phonon modes affects absorption and emission differently, suggesting a complex interaction with both Herzberg–Teller and Franck– Condon coupling present. Detailed understanding of the fundamental electronic processes governing the optical response will help the tailored chemical design of nanocarbon optical devices, via gap tuning and side-chain functionalisation. The authors demonstrate that the band structure of graphene nanoribbons is modulated by cove edges, brightening the luminescence 4-fold via emission from otherwise dark twilight states. High spectral resolution of the optical response reveals strong vibron-electron coupling [ABSTRACT FROM AUTHOR]

Helical nanographenes with high quantum yields and strong chiroptical responses are pivotal for developing circularly polarized luminescence (CPL) materials. Here, we present the successful synthesis of novel π-extended double [7]helicenes (ED7Hs) where two helicene units are fused at the meta- or para-position of the middle benzene ring, respectively, as the structural isomers of the reported ortho-fused ED7H. The structural geometry of these ED7Hs is clearly characterized by single-crystal X-ray analysis. Notably, this class of ED7Hs exhibits bright luminescence with high quantum yields exceeding 40 %. Through geometric regulation of two embedded [7]helicene units from ortho-, meta- to para-position, these ED7Hs display exceptional amplification in chiroptical responses. This enhancement is evident in a remarkable approximate fivefold increase in the absorbance and luminescence dissymmetry factors (g abs and g lum ), respectively, along with a boosted CPL brightness up to 176 M -1  cm -1 , surpassing the performance of most helicene-based chiral NGs. Furthermore, DFT calculations elucidate that the geometric adjustment of two [7]helicene units allows the precise alignment of electric and magnetic transition dipole moments, leading to the observed enhancement of their chiroptical responses. This study offers an effective strategy for magnifying the CPL performance in chiral NGs, promoting their expanded application as CPL emitters., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR (pGNR) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor (P1) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds (1 a, 1 b) containing the same pore size as the shortcuts of pGNR, are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π-π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)