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Azulene, known for its unique electronic properties and structural asymmetry, serves as a promising building block for the design of novel non-benzenoid polycyclic aromatic hydrocarbons (PAHs). Herein, we present the synthesis, characterization, and physical properties of three diazulene-fused heptacyclic aromatic hydrocarbons, 8,17-dioctyldiazuleno[2,1-a:2',1'-h]anthracene (trans configuration), 16,18-dioctyldiazuleno[2,1-a:1',2'-j]anthracene (cis configuration) and 3,18-dioctyldiazuleno[2,1-a:1',2'-i]phenanthrene (zigzag configuration). Three compounds are configurational isomers with different fusing patterns of aromatic rings. All three isomers exhibit pronounced aromaticity, as revealed by nuclear magnetic resonance spectroscopy and theoretical calculations. They exhibit characteristics of both azulene and benzenoid PAHs and are much more stable than their all-benzene analogues. The optical and electrochemical properties of these three isomers were investigated through UV-vis absorption spectra and cyclic voltammetry, revealing distinct behaviors influenced by their molecular configurations. Furthermore, the isomer in trans configuration exhibits promising semiconducting properties with a hole mobility of up to 0.22 cm2 V-1 s-1, indicating its potential in organic electronics applications.
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Photoacid generators (PAGs) are important components of chemically amplified resists. The properties of PAGs directly affect the sensitivity of photoresists, line edge roughness, and resolution. Understanding the photoacid generation process in extreme ultraviolet (EUV) and electron beam (EB) lithography is helpful for photoresist design. However, the microscopic mechanisms remain largely unclear and the large variety in the molecular structure of PAGs presents a challenge to overcome. In this work, we investigate the microscopic processes of photoacid production of ionic PAGs for EUV and EB lithography. The PAG dissociation pathway is found to depend on the molecular structure and conformations. The processes of photoacid production and by-product generation are also revealed. The results contribute to a better understanding of the photochemical reactions in EUV and EB lithography, providing insights into the molecular design of novel PAGs and photoresists.
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The construction of material prediction models using machine learning algorithms can aid in the polyimide structural design and screening of materials as well as accelerate the development of new materials. There is a lack of research on predicting the optical properties of polyimide materials and the interpretation of the structural features. Here, we collected 652 polyimide molecular structures and used seven popular machine learning algorithms to predict the glass transition temperature and cut-off wavelength of polyimide materials and extract key feature information of repeating unit structures. The results showed that the root mean square error of the glass transition temperature prediction model was 33.92 °C, and the correlation coefficient was 0.861. The root mean square error of the cut-off wavelength prediction model was 17.18 nm, and the correlation coefficient was 0.837. The elasticity of the molecular structure was also found to be the key factor affecting glass transition temperature, and the presence and location of heterogeneous atoms had a significant effect on the cut-off wavelengths. Finally, eight polyimide materials were synthesized to test the accuracy of the prediction models, and the experimental characterization values agreed with the predicted values. The results would contribute to the development of polyimide structural design and materials preparation for flexible display.
Assuntos
Algoritmos , Vidro , Aprendizado de Máquina , Temperatura , Temperatura de TransiçãoRESUMO
ConspectusAzulene, an isomer of naphthalene, is a molecule of historical interest for its unusual photophysical properties, including a beautiful blue color derived from the narrow HOMO-LUMO energy gap and anti-Kasha fluorescence from S2 to S0. More recently, it has attracted increasing attention for its novel electronic structure, including an electron-rich five-membered ring and an electron-deficient seven-membered ring with a dipole moment of 1.08 D resulting from resonance delocalization, its different reactivities at odd and even positions, and its stimuli-responsive behavior. As a key building block, azulene has been used in various fields because of its unique physicochemical properties. Recent studies have demonstrated the great potential of azulene for constructing advanced organic materials. However, exploring azulene-based materials has long been hindered by challenges in molecular design and synthesis. Most of the reported azulene-based materials have the azulene unit incorporated through the five-membered ring or seven-membered ring. Creating azulene-based novel building blocks for optoelectronics and using 2,6-connected azulene units to construct conjugated polymers that can adequately utilize the "donor-acceptor" structure of azulene remained underexplored before our contributions. Besides, for most azulene-fused polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics, the azulene substructures were created during later synthesis stages, and the use of azulene derivatives as starting materials to design and synthesize PAHs and heteroaromatics intelligently is still limited.In this Account, we summarize our efforts on the design, synthesis, and applications of azulene-based π-functional materials. Our studies start with the creation of novel π-conjugated structures based on azulene. The design strategy, synthesis, and optoelectronic performance of the first class of azulene-based aromatic diimides, 2,2'-biazulene-1,1',3,3'-tetracarboxylic diimide (BAzDI) and its π-extended and π-bridged derivatives, are presented. Notably, antiparallel stacking between adjacent azulene units derived from azulene's dipole was observed in single crystals of BAzDI and its derivatives. Besides, we developed an azulene-fused isoindigo analogue, azulenoisoindigo, which combines the merits of both isoindigo and azulene, including reversible redox behavior and reversible proton responsiveness. Then we discuss our contributions to the design and synthesis of 2,6-azulene-based conjugated polymers. By incorporation of 2,6-connected azulene units into the polymeric backbone, two conjugated polymers with high organic field-effect transistor (OFET) performance were developed. Two 2,6-azulene-based polymers with proton responsiveness and high electrical conductivity upon protonation were also provided. We also discuss our recent studies on azulene-based heteroaromatics. Two azulene-fused BN-heteroaromatics were designed and synthesized, and they exhibited a selective response to fluoride ion and unexpected deboronization upon the addition of trifluoroacetic acid. An unexpected synthesis of azulene-pyridine-fused heteroaromatics (Az-Py) by reductive cyclization of 1-nitroazulenes and the OFET performance of Az-Py-1 are included. Afterward, we discuss several examples of azulene-capped organic conjugated molecules. The molecules capped with the five-membered ring of azulene favor hole transport, whereas the ones capped with the seven-membered ring favor electron transport.
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Azulene, a nonbenzenoid bicyclic aromatic hydrocarbon with unique electronic structure, is a promising building block for constructing nonbenzenoid π-conjugated systems. However, azulene-fused (hetero)aromatics remain rare as a result of limited synthetic methods. We report herein the unexpected synthesis of azulene- and pyridine-fused heteroaromatics Az-Py-1, a seven fused ring system with 30π electrons, by reductive cyclization of a 1-nitroazulene. The structure of Az-Py-1 was unambiguously confirmed by single-crystal X-ray analysis, and analogues Az-Py-2-Az-Py-6 were also synthesized, demonstrating that this is an effective method for constructing azulene- and pyridine-fused heteroaromatics. Theoretical calculations and photophysical and electrochemical studies of Az-Py-1-Az-Py-6 suggest their potential as semiconductors, and the single-crystal ribbons of Az-Py-1 show high hole mobilities up to 0.29 cm2 V-1 s-1.
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Azulene, a nonalternant bicyclic aromatic hydrocarbon, has unique chemical and physical properties and is considered to be a promising building block for constructing novel polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics. We present here the first two azulene-based BN-heteroaromatics Az-BN-1 and Az-BN-2. The chemical structures and optical and electrochemical properties of both compounds have been investigated, as well as their sensing behavior in response to fluoride ion. Az-BN-1 and Az-BN-2 show different photophysical properties from other reported BN-embedded PAHs, such as lower band gaps and unusual fluorescence. In addition, Az-BN-1 and Az-BN-2 exhibit unexpected deboronization upon addition of trifluoroacetic acid, which distinguishes them from other reported BN-heteroaromatics and can be ascribed to the unique property of the azulene unit.
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Chirality, as a fundamental symmetry property, plays an important role in molecular assembly in the solid state, impacting upon the properties and performance of organic materials. Here, heterochiral assembly was observed upon a binaphthol-based axially chiral material in the thin film state, where the heterochiral assemblies of racemic mixtures exhibit superior crystallization behavior and film morphologies than their homochiral counterparts. Additionally, a dramatic increase (nearly 2 orders of magnitudes) in electronic mobility was obtained upon switching the active layers of organic thin-film transistors from homochiral assemblies to heterochiral assemblies. This work not only gives insights into the structure-aggregation property relationships of axially chiral self-assemblies but also offers new opportunities for novel organic soft materials.
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Azulene as a potential building block for constructing organic/polymeric conjugated materials has attracted more and more attention due to its unique chemical structure and physicochemical properties. However, up to now, most reported azulene-based conjugated polymers have been dominated by the connection of the five-membered ring of azulene through 1,3-positions. Herein, by incorporating 1,3-free-2,6-connected azulene units into the polymeric backbone, two azulene-based all-carbon conjugated polymers P1 and P2 with different connection ways of 2,6-azulene and 2,7-fluorene units were presented. Protonation of these two polymers with trifluoroacetic acid leads to rapid and reversible color changes in both the solution and thin-film state. Moreover, these 1,3-free-2,6-connected azulene-based conjugated polymers exhibit high electrical conductivity (2.94 and 0.32 S/cm for P1 and P2, respectively) in thin film when doped by trifluoromethanesulfonic acid.
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Layered O3-type sodium oxides (NaMO2 , M=transition metal) commonly exhibit an O3-P3 phase transition, which occurs at a low redox voltage of about 3â V (vs. Na+ /Na) during sodium extraction and insertion, with the result that almost 50 % of their total capacity lies at this low voltage region, and they possess insufficient energy density as cathode materials for sodium-ion batteries (NIBs). Therefore, development of high-voltage O3-type cathodes remains challenging because it is difficult to raise the phase-transition voltage by reasonable structure modulation. A new example of O3-type sodium insertion materials is presented for use in NIBs. The designed O3-type Na0.7 Ni0.35 Sn0.65 O2 material displays a highest redox potential of 3.7â V (vs. Na+ /Na) among the reported O3-type materials based on the Ni2+ /Ni3+ couple, by virtue of its increased Ni-O bond ionicity through reduced orbital overlap between transition metals and oxygen within the MO2 slabs. This study provides an orbital-level understanding of the operating potentials of the nominal redox couples for O3-NaMO2 cathodes. The strategy described could be used to tailor electrodes for improved performance.
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Azulene is a promising candidate for constructing optoelectronic materials. An effective strategy is presented to obtain high-performance conjugated polymers by incorporating 2,6-connected azulene units into the polymeric backbone, and two conjugated copolymers P(TBAzDI-TPD) and P(TBAzDI-TFB) were designed and synthesized based on this strategy. They are the first two examples for 2,6-connected azulene-based conjugated polymers and exhibit unipolar n-type transistor performance with an electron mobility of up to 0.42â cm2 V-1 s-1 , which is among the highest values for n-type polymeric semiconductors in bottom-gate top-contact organic field-effect transistors. Preliminary all-polymer solar cell devices with P(TBAzDI-TPD) as the electron acceptor and PTB7-Th as the electron donor display a power conversion efficiency of 1.82 %.
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Azulene, as an isomer of naphthalene, has received increasing interest due to its unique chemical structure and unusual photophysical properties, including a large dipole moment of 1.08â D, a narrow energy gap between the HOMO and LUMO, and abnormal fluorescence (anti-Kasha's rule) from the second excited state to the ground state. In this Minireview, the general strategies and representative synthetic methods for the preparation and functionalization of azulene and its derivatives are presented, and then the application of azulene-based optoelectronic materials in organic field-effect transistors and solar cells is discussed. Finally, the challenges and outlook on developing azulene-based optoelectronic materials are discussed, together with several key points on molecular design and synthesis.
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Azulene, a 10-π-electron isomer of naphthalene, is a nonbenzenoid bicyclic aromatic hydrocarbon with a beautiful blue color and a large dipole moment. We present here the first class of azulene-based aromatic diimides, 2,2'-biazulene-1,1',3,3'-tetracarboxylic diimides (BAzDIs), which comprise a 2,2'-biazulene moiety and two seven-membered imide groups. DFT calculations, thermal, optical and electrochemical properties of two BAzDI derivatives as well as single crystal analysis and the charge transport behavior were studied. The results demonstrate that BAzDIs have unique photophysical properties and are promising for organic electronic materials.