Article
Chemistry, Multidisciplinary
Qing Jiang, Haipeng Wei, Xudong Hou, Chunyan Chi
Summary: In this study, the successful synthesis of the largest Circumacene (CA) molecule to date, named 1, was reported. Its structure was confirmed by X-ray crystallographic analysis and its electronic properties were systematically investigated. It exhibited a unique open-shell diradical character with extended zigzag edges and showed dominant local aromatic character with π-electrons delocalized in the individual aromatic sextet rings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jiaxiang Guo, Zeyi Li, Xinyu Tian, Tianyu Zhang, Yue Wang, Chuandong Dou
Summary: We report the synthesis of B/N-type organic diradicaloids with atom-precise control over open-shell nature through quinoidal pi-extension of a B/N-heterocycle. These diradicaloids exhibit modulated (anti)aromaticity and enhanced diradical characters compared with all-carbon analogues, and display intriguing properties such as magnetic activities and highly red-shifted absorptions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Qing Jiang, Yi Han, Ya Zou, Chunyan Chi
Summary: Here, we report the synthesis and redox properties of two new quinodimethane-embedded expanded [11]- and [13]helicenes. These helicenes exhibit unique electronic properties with small energy gaps and amphoteric redox behavior. Furthermore, their dications and dianions show significant open-shell singlet diradical character with small singlet-triplet energy gaps.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Nico Zeitter, Nikolai Hippchen, Steffen Maier, Frank Rominger, Andreas Dreuw, Jan Freudenberg, Uwe H. F. Bunz
Summary: A long-lived, soluble heptacene and a persistent tetrabenzononacene were synthesized through sixfold TIPS-ethynylation combined with fourfold bromination and pi-extension via Stille coupling. The stability of both compounds was enhanced by double TIPS-ethynylation on every other benzene ring. The ambipolar transistor material tetrabromoheptacene showed good performance, with a n-channel mobility of up to 0.036 cm(2)V-1s-1, as confirmed by the generation of its monoanion and monocation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xuan Yang, Frank Rominger, Michael Mastalerz
Summary: Longer acenes with more than six linearly fused six-membered rings have unique photophysical properties and high potential for organic electronics applications, but they rapidly lose chemical stability as size increases. Stabilization approaches involving bulky or electron-withdrawing groups and peri-annulation have been used to stabilize these compounds. Peri-annulated compounds, although no longer real acenes, also exhibit fascinating properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Medicinal
Adrien Varet, Nicolas Prcovic, Cyril Terrioux, Denis Hagebaum-Reignier, Yannick Carissan
Summary: The BenzAI program can automatically generate benzenoids with defined structural constraints and extract IR spectra for benzenoids with less than 10 rings. It can also compute local aromaticity for closed-shell and monoradical species.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2022)
Article
Chemistry, Multidisciplinary
Chengguo Yan, Weiwei Ding, Gang Zhang
Summary: Besides peripheral modification, the introduction of heteroatoms to modify the property of longer acenes with improved chemical stability has been extensively studied. However, the use of 4-pyridone to enhance the stability of higher acenes has not been achieved yet. In this study, we successfully synthesized a series of monopyridone-doped acenes up to heptacene via the palladium-catalyzed Buchwald-Hartwig amination. The effect of pyridone on the properties of doped acenes was investigated experimentally and computationally, showing enhanced stability and electronic communication between acene planes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yoann Olivier, Juan-Carlos Sancho-Garcia
Summary: New heterocyclic diradicaloids with open-shell ground states are obtained by extending the structure and quinoidal properties of boron and nitrogen-doped polycyclic systems, combining the advantages of both design strategies. Experimental characterization and theoretical calculations reveal their electronic structure and explain their magnetic and photophysical properties, expanding the range of molecular templates available for cutting-edge applications in organic electronics and spintronics.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Luis Leyva-Parra, Ricardo Pino-Rios, Diego Inostroza, Miquel Sola, Mercedes Alonso, William Tiznado
Summary: This study investigates the connection between Clar's rule, aromaticity, and magnetic properties of polycyclic benzenoid hydrocarbons using magnetically induced current density analysis. The results reveal the presence of a global ring current in the analyzed polycyclic systems, aligning with Clar's aromatic pi-sextets only in cases involving migrating pi-sextet structures.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jiaxiang Guo, Yue Yang, Chuandong Dou, Yue Wang
Summary: Organic diradicaloids have unique open-shell structures and properties, and introducing boron atoms into their structures can enhance their stability and lead to intriguing magnetic and optoelectronic properties. The B-containing organic diradicaloids reported in this article exhibit excellent ambient stability, open-shell singlet diradical structures, and unique Lewis acidity, demonstrating promising potential for novel applications in organic electronics and spintronics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
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, Organic
Qi Xu, Chu Wang, Dan Zheng, Jing He, Ying Wang, Xuebo Chen, Hua Jiang
Summary: A new type of distorted nanographene was successfully designed and synthesized using Diels-Alder and Scholl reactions, featuring a unique structure with a dibenzobistetracene core and corannulene units. The study also investigated the photophysical properties and (non)aromaticity of the nanographene through absorption and emission spectra combined with theoretical calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
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, Multidisciplinary
Mikhail Feofanov, Dominik Lungerich, Vladimir Akhmetov, Konstantin Amsharov
Summary: A facile approach to synthesize two-dimensional acenes dimers, exemplified by 2,3,8,9-dibenzanthanthrene (DBATT) connected via rigid linker, was reported in this study. The technique, utilizing dehydrative pi-extension on the last step of synthesis, was shown to be applicable for the synthesis of DBATT dimers connected rigidly with conjugated and non-conjugated linkers.
