Article
Chemistry, Multidisciplinary
Yumeng Guo, Herdya S. Torchon, Yikun Zhu, Zheng Wei, Zhenyi Zhang, Haixiang Han, Marina A. Petrukhina, Zheng Zhou
Summary: This study investigates the chemical reactivity of a fullerene fragment with alkali metals using truxene as a model. The results demonstrate the dependence of core curvature on charge and alkali metal coordination. Additionally, the deprotonation process introduces aromaticity and pi-conjugation, resulting in changes in the optical properties.
Article
Chemistry, Multidisciplinary
Ranran Li, Bin Ma, Shengtao Li, Chongdao Lu, Peng An
Summary: This article describes a series of chalcogen-doped nanographenes and their oxides. The molecular design of these nanographenes is based on the insertion of different chalcogens into the hexa-peri-hexabenzocoronene backbone. The nonplanar conformations of these nanographenes, except for the oxygen-doped one, exhibit better solubility compared to the planar hexa-peri-hexabenzocoronene. Single-crystal X-ray diffractometry confirms the three-dimensional structures of these nanographenes. The photophysical properties of each structure, including UV-vis absorption, fluorescence, chiroptical, charge distribution, and orbital gaps, are investigated experimentally or theoretically. The properties are significantly influenced by the doped chalcogen and its oxidative state. It is noteworthy that the selenium-doped nanographene or its oxide undergoes a selenium extrusion reaction to form hexa-peri-hexabenzocoronene quantitatively upon heating or adding an acid, which can be considered as precursors of hydrocarbon hexa-peri-hexabenzocoronene.
Article
Chemistry, Organic
Matthias Schnitzlein, Carina Mutzel, Kazutaka Shoyama, Jeffrey M. Farrell, Frank Wurthner
Summary: In this study, a series of heptagon-extended corannulenes were synthesized using Pd-catalyzed [5+2] annulation from a borinic acid precursor obtained by C-H borylation strategy. Single-crystal X-ray analysis revealed the presence of two conformational enantiomers crystallizing in a racemic mixture. Theoretical calculations were employed to elucidate their optoelectronic properties and aromaticity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shangshang Wang, Min Tang, Lin Wu, Lifang Bian, Liang Jiang, Jiali Liu, Zheng-Bin Tang, Yimin Liang, Zhichang Liu
Summary: A new modular approach for the synthesis of various azulene compounds with narrow band gaps and high stability has been developed, showing enhanced near-infrared fluorescence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yushi Ohno, Shogo Ando, Daisuke Furusho, Ryoyu Hifumi, Yuuya Nagata, Ikuyoshi Tomita, Shinsuke Inagi
Summary: Here, a facile and selective synthesis of cationic azatriphenylene derivatives was achieved through electrochemical intramolecular cyclization, where the key step involves atom-economical C-H pyridination without a transition-metal catalyst or an oxidant. This proposed strategy provides a practical approach for introducing cationic nitrogen (N (+)) into pi-electron systems, thus expanding the molecular design of N (+)-doped polycyclic aromatic hydrocarbons.
Article
Multidisciplinary Sciences
Jovana Stanojkovic, Ronny William, Zhongbo Zhang, Israel Fernandez, Jingsong Zhou, Richard D. Webster, Mihaiela C. Stuparu
Summary: The authors demonstrate that mechanochemical Scholl reaction provides a direct route to chlorinated curved nanographenes from graphitization precursors. The chlorination is regioselective, high-yielding, and general. The resulting nanographenes can be chemically modified with precision through Suzuki or nucleophilic aromatic substitution reactions, leading to modulation of material properties via edge modification.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Wenting Sun, Yue Yang, Xinyu Tian, Liuzhong Yuan, Yue Wang, Chuandong Dou
Summary: B/N-codoped polycyclic aromatic hydrocarbons (PAHs) were constructed by combining the B- and N-doped π-systems, enabling tunable structures and optical properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Yan-Ying Wu, Yi-Lin Wu, Cheng-Lan Lin, Hung-Cheng Chen, Yao-Yuan Chuang, Chih-Hsien Chen, Chih-Ming Chou
Summary: A strategy for the synthesis of dibenz-[a,j]-anthracenes (DBAs) from cyclohexa-2,5-diene-1-carboxylic acids is presented. The method involves sequential C-H olefination, cycloaddition, and decarboxylative aromatization, leading to regioselective ring formation and functional group introduction.
Article
Chemistry, Physical
Slavko Radenkovi, Zeljko Tomovi
Summary: A detailed study on the geometry, aromatic character, electronic and magnetic properties of positively charged N-doped polycyclic aromatic hydrocarbons (PAHs) was conducted. Magnetic properties were analyzed using the magnetically induced current density method. Comparative studies on local aromaticity were performed using different indices. The presence of N-atoms caused planarity distortion in the studied N-doped systems. Geometric changes and charged nature did not significantly affect current density and local aromaticity compared to parent benzenoid hydrocarbons. This study demonstrates the use of quantum chemical calculations in the design and fine tuning of PAH properties.
Review
Environmental Sciences
Meng Qiao, Weixiao Qi, Huijuan Liu, Jiuhui Qu
Summary: Oxygenated polycyclic aromatic hydrocarbons (OPAHs) have higher concentrations and toxicity in water environments, posing significant ecological risks to surface water ecosystems.
ENVIRONMENT INTERNATIONAL
(2022)
Article
Chemistry, Physical
Thomas Liu, Baptiste Carles, Christine Elias, Claire Tonnele, Daniel Medina-Lopez, Akimitsu Narita, Yannick Chassagneux, Christophe Voisin, David Beljonne, Stephane Campidelli, Loic Rondin, Jean-Sebastien Lauret
Summary: In this study, we conducted single-molecule spectroscopy at cryogenic temperatures to investigate the optical properties of graphene quantum dots (GQDs). We found that temperature has an effect on the spectral characteristics of GQDs, and we used density functional theory calculations to explain these observations. Additionally, we discovered that the vibrational features can serve as a unique fingerprint for identifying GQDs.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Multidisciplinary Sciences
Yusuke Nakakuki, Takashi Hirose, Hikaru Sotome, Min Gao, Daiki Shimizu, Ruiji Li, Jun-Ya Hasegawa, Hiroshi Miyasaka, Kenji Matsuda
Summary: Helically twisted conductive nanocarbon materials are suitable for optoelectronic and electromagnetic molecular devices on the nanometer scale, showing a large effective conjugation length and ultrafast decay dynamics. The extended π-helicenes achieved a large effective conjugation length through helical fusion, leading to an absorption edge in the near-infrared region.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiushang Xu, Amy L. Vonder Haar, Rengo Yoshioka, Qizheng Zhang, Serhii Vasylevskyi, Andrew J. Musser, Akimitsu Narita
Summary: A benzo[rst]pentaphene derivative, BPP-MeOPA, was synthesized and characterized by NMR and single-crystal X-ray analysis. Investigation of its photophysical properties, including transient absorption spectroscopy, revealed improved absorption and emission features from an S-1 state with excitonic and charge-transfer character by introducing MeOPA groups.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Laiyun Zhou, Boming Wu, Yuanyuan Chen, Jianye Gong, Jianguo Wang, Gaole Dai, Chunyan Chi, Qing Wang
Summary: A nitrogenated derivative of Ovalene with all zigzag edges and nitrogen atom doping at the periphery has been successfully developed through one-step nitrogenation of formylbisanthene. These molecules exhibit decreased highest occupied molecular orbital levels, enhanced intermolecular interactions, and reversible acid response due to nitrogen incorporation. Additionally, the aza-ovalene also shows a diatropic ring current along the periphery, providing rare examples of all-zigzag-edged N-polycyclic aromatic hydrocarbons.
Article
Chemistry, Inorganic & Nuclear
Huimin Zhong, Cong Jiang, Jiahui Zou, Guancheng Zhu, Yanyan Huang
Summary: In this study, CeO2-based porous carbonaceous frameworks (CeO2 PCFs) were used as antioxidant nanozymes to scavenge reactive oxygen species and absorb benzo[a]pyrene. CeO2 PCFs exhibited excellent superoxide dismutase-like and catalase-like activity, effectively eliminating superoxide radical, hydroxyl radical, and hydrogen peroxide. The 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) free radical scavenging assay confirmed the free radical scavenging ability of CeO2 PCFs. Furthermore, CeO2 PCFs with large surface area and porous structure efficiently adsorbed benzo[a]pyrene. The designed CeO2 PCFs can serve as new antioxidant nanozymes for scavenging reactive oxygen species and adsorbing polycyclic aromatic hydrocarbons (PAHs).
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jie Zeng, Jiaying Su, Feiying You, Jun Zhu
Summary: It is found that methyleneboranes without any substituent at the boron atom perform best on dinitrogen activation due to their small singlet-triplet gap. Strong correlations are achieved between the singlet-triplet energy gap and the reaction energies for the formation of end-on and side-on products. Methyleneboranes can mimic transition metals to cleave the N=N triple bond, which is important for experimental chemists studying dinitrogen activation by main group species.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Feiying You, Rulin Qiu, Jun Zhu
Summary: This study used density functional theory (DFT) calculations to discover that osmapentalene and osmapyridinium complexes can exhibit adaptive aromaticity in both the S-0 and T-1 states, supported by various aromaticity indices. This finding expands the concept of adaptive aromaticity and invites experimental chemists to verify and enrich the field of aromatic organometallic chemistry.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shicheng Dong, Jun Zhu
Summary: This study demonstrates the feasibility of metal-free activation of dinitrogen under mild conditions using a dual Lewis acid (DLA) through density functional theory (DFT) calculations. The DLA is also capable of activating a series of small molecules. The study highlights the importance of aromaticity in stabilizing intermediates and products. These findings provide an alternative approach to N-2 activation and functionalization, showcasing the potential of DLA for small molecule activation.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Qin Zhu, Shuoqi Zhang, Jing Ma, Jun Zhu, Shuhua Li, Guixiang Zeng
Summary: The transfer hydrogenation of azobenzene with ammonia borane mediated by pincer bismuth complex 1 was studied using density functional theory calculations. The study revealed an unusual metal-ligand cooperation mechanism involving the saturation/regeneration of the C=N functional group on the pincer ligand. The reaction proceeds through the hydrogenation of the C=N bond, followed by the conversion of 3(CN) to a Bi-H intermediate, and eventually results in the production of N,N'-diphenylhydrazine and regeneration of the catalyst. The substitution of the phenyl group with a tert-butyl group on the pincer ligand improves the catalyst's performance.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yang-Yang Ju, Ling Chai, Kang Li, Jiang-Feng Xing, Xiao-Hui Ma, Zhen-Lin Qiu, Xin-Jing Zhao, Jun Zhu, Yuan-Zhi Tan
Summary: In this study, two trilayer nanographenes were synthesized by covalently linking nanographene layers through helicene bridges, and their compact trilayer-stacked architecture was characterized. By introducing a furan ring into the helicene linker, the interlayer overlap and pi-conjugation of the trilayer nanographenes can be modulated, enabling tunable interlayer coupling. The synthesized trilayer nanographenes exhibit rigid chirality transfer from the helicene moiety to the stacked nanographene layers, representing covalently linked multilayer nanographenes with a tunable multilayer stacking structure.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Qianqian Deng, Jiaying Su, Jun Zhu
Summary: In this study, density functional theory calculations were used to investigate the origin of adaptive aromaticity in metallapyridiniums. The results revealed that the strength of metal-carbon and metal-nitrogen bonds, as well as the blocking of spin delocalization, play crucial roles in achieving aromaticity in the lowest triplet state of metallapyridiniums. The ligand effects on adaptive aromaticity in metallapyridiniums were also examined.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Yishi Wu, Lina Lu, Buyang Yu, San Zhang, Pengdong Luo, Mingxing Chen, Jingping He, Yongyao Li, Chunfeng Zhang, Jun Zhu, Jiannian Yao, Hongbing Fu
Summary: In this study, an unconventional SF system with excited-state aromaticity was investigated using time-resolved spectroscopy. The authors found that the population transfer occurs by a time-dependent exothermic process driven by coherent coupling between electronic and spin degrees of freedom, leading to the formation of free triplets. These findings provide important insights into the SF mechanism and can guide the development of efficient and stable SF materials for practical applications.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Review
Multidisciplinary Sciences
Qin Zhu, Shuwen Chen, Dandan Chen, Lu Lin, Kui Xiao, Liang Zhao, Miquel Sola, Jun Zhu
Summary: This review highlights the relationship between aromaticity and reaction mechanism, emphasizing the importance of computational chemistry in understanding aromaticity-driven reactions. Aromatizing a transition state/product or destabilizing a reactant by antiaromaticity can promote specific reactions. The article also discusses various specific reaction examples, including small-molecule activation, bond activation, rearrangement, and metathesis reactions.
FUNDAMENTAL RESEARCH
(2023)
Article
Chemistry, Inorganic & Nuclear
Qingfu Ye, Yifei Fang, Jun Zhu
Summary: Complexes with adaptive aromaticity, which possess aromaticity in both the S0 and T1 states, are rare. In this study, we show that 18e metallapentalenes can exhibit adaptive aromaticity when nitrido and imido ligands are introduced. The strength of the metal-carbon bond is found to play a crucial role in S0 state aromaticity, while T1 state aromaticity is attributed to spin electron localization. These findings are valuable for the development of metallaaromatic chemistry.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shuwen Chen, Jun Zhu
Summary: The use of UV light limits the applications of heteroarylazos and azobenzenes, especially in biomedicine and photopharmacology. In this study, we systematically investigated the relationship between anti-aromaticity and the absorption spectra of a series of heterocyclic azos using density functional theory calculations. We demonstrated that antiaromatic heterocycles substituted with diazenes enable significant red shifts of the absorption spectra of E and Z isomers, and the introduction of substituents further tunes the absorption. Ultimately, we achieved absorption of the first transition bands of E and Z isomers of azos in the near-infrared region.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Qingfu Ye, Jun Zhu
Summary: Aromaticity is an important concept in chemistry that has attracted significant attention from both experimental and computational chemists. The harmonic oscillator model of aromaticity (HOMA) is a reliable criterion for evaluating aromaticity based on bond distance, with negligible computational cost. However, there is a lack of HOMA parameters for organometallic aromatics. In this study, the researchers developed a new HOMA parameter for Os-C bonds in organometallic compounds, which showed good correlation with other aromaticity indices.
Article
Materials Science, Multidisciplinary
Zuyuan Liu, Long Wang, Qianqian Deng, Jun Zhu, Jing Sun, Hua Wang, Hongbing Fu, Jiannian Yao
Summary: Singlet fission (SF) is a potential approach to boost the conversion efficiency of solar cells. However, the limited availability of suitable SF materials hinders its practical applications. This study introduces a new SF material based on a rubicene (Rc) skeleton, which demonstrates broad absorption, suitable energy levels, efficient SF process, and excellent stability.
ACS MATERIALS LETTERS
(2023)
Article
Chemistry, Physical
Alvi Muhammad Rouf, Jun Zhu
Summary: This article discusses the stability of 1H-azirine and its unconventional stabilization route using the precursor 2H-azirine, which exploits electronic and steric elements.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Jiahao Rao, Shicheng Dong, Chengbo Yang, Qing Liu, Xuebing Leng, Dongyang Wang, Jun Zhu, Liang Deng
Summary: Tuning the spin state of metal carbynes is a challenging task in chemistry. We have synthesized the first triplet metal terminal carbyne, which exhibits unique reactivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Qianqian Deng, Sajid Imran, Jun Yan, Jun Zhu
Summary: This study demonstrates through density functional theory calculations that the cyclobutadiene (CBD) ring could exhibit dual antiaromaticity in the lowest singlet and triplet states. It also identifies the localization of spin density on the substituent as the key factor in maintaining antiaromaticity in the triplet state.
ORGANIC CHEMISTRY FRONTIERS
(2023)
