Review
Chemistry, Organic
David I. H. Maier, Barend C. B. Bezuidenhoudt, Charlene Marais
Summary: The dibenzo[b,f]azepine skeleton is of great significance in the pharmaceutical industry due to its use in existing antidepressants, anxiolytics, and anticonvulsants, as well as its potential in other applications such as organic light emitting diodes and dye-sensitized solar cell dyes. This review provides an overview of the synthetic strategies for dibenzo[b,f]azepines and other dibenzo[b,f]heteropines, as well as their applications in different fields.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Piotr Tobiasz, Filip Borys, Marta Borecka, Hanna Krawczyk
Summary: The study discussed the synthesis of photoswitchable azo-dibenzo[b,f]oxepine derivatives and microtubule inhibitors using a concise method and analyzed the products using experimental and theoretical methods. Additionally, the E/Z isomerization of the derivatives was evaluated and found to be controllable through photochemical means with visible-wavelength light.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Biochemistry & Molecular Biology
Filip Borys, Piotr Tobiasz, Jakub Sobel, Hanna Krawczyk
Summary: Dibenzo[b, f]oxepine derivatives are an important scaffold in natural medicinal chemistry, and their interaction with the colchicine binding site in tubulin has been analyzed. The geometry of E/Z isomers and the HOMO-LUMO gap have been calculated, and the potential application of these derivatives in photopharmacology has been explored.
Article
Chemistry, Applied
Xin-Chen Zhan, Guo-Qiang Lin, Jian-Guo Fu, Xiao-Ming Ji, Shu-Sheng Zhang, Chen-Guo Feng
Summary: A cascade [4+3] annulation of o-alkenyl bromoarenes and o-bromoaniline derivatives is reported, leading to the synthesis of various dibenzo[b,f]azepines with substitutions on the 10/11 position in moderate to high yields. The versatility of this protocol is demonstrated through the preparation of a precursor for the drug molecule oxcarbazepine, gram-scale synthesis, and two product transformations. Unlike previous amination/Heck sequences, this cascade process follows a C(vinyl), C(aryl)-palladacycle involved pathway.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Biochemistry & Molecular Biology
Hanna Krawczyk
Summary: In this review, various issues related to dibenzo[b,f]oxepine derivatives are discussed. The dibenzo[b,f]oxepine scaffold is an important framework in medicinal chemistry and is found in several medicinally relevant plants. This manuscript addresses topics such as the extraction of dibenzo[b,f]oxepines from plants and their significance in medicine, the biosynthesis of dibenzo[b,f]oxepines, the active synthetic derivatives, their potential as microtubule inhibitors, and the future applications of dibenzo[b,f]oxepine derivatives. Overall, this review provides insights into the structural features and pharmacological actions of dibenzo[b,f]oxepine derivatives.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Organic
Kaili Li, Kun Zhang, He Huang, Qianqian Zhang, Chuanjun Song, Junbiao Chang
Summary: An efficient base-promoted intramolecular O-arylation method has been developed for the synthesis of dibenzo[b,f]oxepinones from 2-halobenzyl 2-hydroxyphenyl ketones, with good to excellent yields. This strategy has also been extended to the total synthesis of dihydroartocarpol D.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Sanjay Yadav, Surisetti Suresh
Summary: In this study, we have demonstrated a novel NHC-catalyzed transformation to access dibenzo-fused seven-membered heterocyclic compounds through intramolecular Stetter reaction at room temperature. Various dibenzo[b,f]oxepine and dibenzo[b,f]thiepine derivatives were obtained in high yields. The 1,4-dicarbonyl functionality of a representative derivative underwent additional heterocyclization via Paal-Knorr reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Takumi Sakamaki, Takayuki Nakamuro, Keitaro Yamashita, Kunio Hirata, Rui Shang, Eiichi Nakamura
Summary: B2N2-DBR and its derivatives were successfully synthesized using a two-step modular synthetic route, showing blue emission with a higher fluorescence quantum yield and stability against water and air but sensitivity to fluoride and pyridine. Interaction with fluoride resulted in a bathochromic shift of emission with retention of high fluorescence quantum yield, while coordination with pyridine quenched its photoluminescence.
CHEMISTRY OF MATERIALS
(2021)
Article
Biochemistry & Molecular Biology
Filip Borys, Piotr Tobiasz, Marcin Poterala, Hanna Fabczak, Hanna Krawczyk, Ewa Joachimiak
Summary: Cancer is a major cause of human death worldwide and various therapies, including chemotherapy, have been developed. Aberrant mitotic spindle in cancer cells leads to genetic instability, and tubulin, the building block of microtubules, is a useful target in anti-cancer research. Colchicine-pocket-binding agents, such as stilbenoids and their derivatives, have shown potential as anti-cancer drugs by disrupting the microtubular cytoskeleton. Systematic studies on the antiproliferative activity of selected compounds reveal the most cytotoxic agents and their interaction with tubulin heterodimers.
Article
Chemistry, Organic
Robert Thoran, Tristan Schuh, Philipp Holling, Florian Puls, Olga Kataeva, Hans-Joachim Knoelker
Summary: The iron-catalyzed oxidative C-C homocoupling of diarylamines provides crucial synthetic building blocks, 2,2'-bis(arylamino)-1,1'-biaryls, for the synthesis of seven-membered heterocyclic ring systems. Reaction with efficient 1,1-dielectrophiles such as paraformaldehyde, diphenyl carbonate, and diphenyl sulfite leads to the formation of dibenzo[d,f][1,3]diazepines, dibenzo[d,f][1,3]diazepinones, and dibenzo[c,e][1,2,7]thiadiazepine 6-oxides. These synthetic procedures offer short and practical routes to these 1,3-diazepine derivatives with mild reaction conditions and high tolerance of various functional groups.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Darren M. Driscoll, Hongjun Liu, Benjamin Reinhart, Ilja Popovs, Vera Bocharova, Santa Jansone-Popova, De-en Jiang, Alexander S. Ivanov
Summary: This study investigates the role of counterions in molecular recognition of lanthanides in rare-earth element separations. The presence of noncoordinating anions leads to a unique coordination sphere structure and self-assembly of the complexes into larger nanoclusters through electrostatic interactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Applied
Yuming Yu, Wei Lan, Xin Wang, Yaqiong Wang, Ming Gao, Xin Xu, Lei Shen, Dou Wang, Duozhi Wang, Ablimit Abdukader, Xiaodong Cai, Zhenjiang Liang, Hui Tan
Summary: In this study, two dibenzo[a,g]corannulene-phenoxazine dyads, BBC-C-PXZ and BBC-N-PXZ, were successfully synthesized and their photoelectrical properties were investigated. Both dyads showed intramolecular charge transfer in solution and aggregated state. They also exhibited moderate to good singlet oxygen quantum yields. The study provides new advances and breakthroughs in the design of organic electronic materials by introducing curved polycyclic aromatic hydrocarbons and diversified linkage positions.
Article
Chemistry, Organic
Yan-Qin He, Zhong-Qiu Li, Yu-Wu Zhong
Summary: A synthetic methodology for the preparation of dibenzo[f,h]quinolines and their derivatives via stepwise ruthenium-catalyzed C-H arylation and potassium-mediated reductive cyclodehydrogenation from 2-phenylpyridine and aryl bromides is described. One dibenzo[f,h]quinoline derivative is used as a bidentate ligand to synthesize a cyclometalated ruthenium complex. The molecular structures of two dibenzo[f,h]quinoline compounds and the ruthenium complex are determined by single-crystal X-ray analysis.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Gang Cheng, Dongdong Tu, Xiang Zuo, Zechen Wu, Bin Wan, Yanghui Zhang
Summary: A novel and straightforward approach for the synthesis of tribenzo[b,d,f]azepines has been developed from 2-iodobiphenyls and 2-bromoanilines. A wide range of products were obtained via a cascade intermolecular palladium-catalyzed C-H activation/dual coupling reaction, with C,C-palladacycles likely being the reaction intermediates.
Article
Chemistry, Physical
Sissembayeva Yana, Soo Kyung Cho, Yoon-Hwae Hwang
Summary: In this study, a dibenzo[b,f][1,5]diazocine/ZnO organic/inorganic hybrid photoanode is proposed for photoelectrochemical water splitting. The hybrid photoanode demonstrates enhanced absorbance, decreased charge recombination, and increased charge separation compared to bare ZnO nanorod arrays. The addition of a platinum nanoparticle cocatalyst further enhances the photocurrent density. These findings suggest that the proposed organic/inorganic hybrid photoelectrode is a promising candidate for efficient solar water splitting.
INTERNATIONAL JOURNAL OF PHOTOENERGY
(2022)
Review
Polymer Science
Kazuo Tanaka, Yoshiki Chujo
Summary: This review introduces a new concept of developing stimuli-responsive luminochromic materials based on frustrated element-blocks. The stimuli-responsive properties and luminescent behaviors of frustrated boron clusters are described. Methods for obtaining materials with unique chromic behaviors, such as designing fused complexes and generating frustrated state by polymerization, are also discussed.
Article
Chemistry, Multidisciplinary
Junki Ochi, Kazuo Tanaka, Yoshiki Chujo
Summary: The unique solid-state excimer emission of three types of acridine-tethered o-carboranes with variable degrees of methylation was reported. The emitted light colors were drastically changed by the steric effect of the methyl groups, with a strong correlation found between the pi-overlapping and excimer character. Variable-temperature PL measurements revealed that these PL species should be in thermal equilibrium at room temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kazuhiro Yuhara, Kazuo Tanaka
Summary: This study reports the luminochromic behaviors of o-carborane-modified anthracene derivatives regarding mechanochromic luminescence (MCL). Crystal polymorphs of bis-o-carborane-substituted anthracene showed dual-emission properties in the solid state, characterized by excimer and charge transfer (CT) emission bands. Compound 1a exhibited bathochromic MCL due to a transition from dual emission to CT emission, while compound 2 displayed hypsochromic MCL resulting from a transition from CT to excimer emission. Additionally, ground 1a showed self-recovery of its luminescent color when left at room temperature.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Materials Science, Multidisciplinary
Takumi Yanagihara, Kazuo Tanaka
Summary: This study presents the unique luminescent properties of pyrene-substituted nido-carborate anion (PYnCA) with two counter cations, NBu4+ and PPh4+. It is found that PYnCA exhibits twisted intramolecular charge transfer (TICT) emission by changing the dihedral angle between pyrene and the C-cage-C-cage bond in the carborane unit. The research also demonstrates the modulation of luminescent species by counter cations in both solution and solid states, showing potential for stimuli-responsive materials.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Organic
Hiroyuki Watanabe, Yoshinori Ito, Kazuo Tanaka, Yoshiki Chujo
Summary: The development of 1,3,4,6,8,9b-hexaazaphenalene (6AP) derivatives with excellent NIR light absorption properties and deep LUMO levels is illustrated. The electron-withdrawing ability of the 8-nitrogen atom in the 6AP scaffold was enhanced by introducing a B-N dative bond. The formation of a boron-nitrogen Lewis acid-base pair strengthened the electron-withdrawing ability and induced the low-lying LUMO levels.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Haoran Wang, Qiyao Li, Parvej Alam, Haotian Bai, Vandana Bhalla, Martin R. Bryce, Mingyue Cao, Chao Chen, Sijie Chen, Xirui Chen, Yuncong Chen, Zhijun Chen, Dongfeng Dang, Dan Ding, Siyang Ding, Yanhong Duo, Meng Gao, Wei He, Xuewen He, Xuechuan Hong, Yuning Hong, Jing-Jing Hu, Rong Hu, Xiaolin Huang, Tony D. James, Xingyu Jiang, Gen-ichi Konishi, Ryan T. K. Kwok, Jacky W. Y. Lam, Chunbin Li, Haidong Li, Kai Li, Nan Li, Wei-Jian Li, Ying Li, Xing-Jie Liang, Yongye Liang, Bin Liu, Guozhen Liu, Xingang Liu, Xiaoding Lou, Xin-Yue Lou, Liang Luo, Paul R. McGonigal, Zong-Wan Mao, Guangle Niu, Tze Cin Owyong, Andrea Pucci, Jun Qian, Anjun Qin, Zijie Qiu, Andrey L. Rogach, Bo Situ, Kazuo Tanaka, Youhong Tang, Bingnan Wang, Dong Wang, Jianguo Wang, Wei Wang, Wen-Xiong Wang, Wen-Jin Wang, Xinyuan Wang, Yi-Feng Wang, Shuizhu Wu, Yifan Wu, Yonghua Xiong, Ruohan Xu, Chenxu Yan, Saisai Yan, Hai-Bo Yang, Lin-Lin Yang, Mingwang Yang, Ying-Wei Yang, Juyoung Yoon, Shuang-Quan Zang, Jiangjiang Zhang, Pengfei Zhang, Tianfu Zhang, Xin Zhang, Xin Zhang, Na Zhao, Zheng Zhao, Jie Zheng, Lei Zheng, Zheng Zheng, Ming-Qiang Zhu, Wei-Hong Zhu, Hang Zou, Ben Zhong Tang
Summary: This review provides a comprehensive summary of the applications of aggregation-induced emission (AIE) luminogens in biological imaging, dynamic physiological processes, disease diagnosis and treatment, and specific analyte detection and monitoring. The review also discusses critical issues and future directions, aiming to promote the development of AIE in the fields of life and health.
Article
Chemistry, Multidisciplinary
Masayuki Gon, Misao Yaegash, Kazuo Tanaka
Summary: This article presents a study on near-infrared luminescent materials. By introducing electron-donating groups, the luminescence properties of these materials were enhanced, and factors affecting their luminescent behavior were identified. These findings are significant for the development of tunable near-infrared luminescent materials.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
Article
Chemistry, Multidisciplinary
Hiromasa Takahashi, Hiroyuki Watanabe, Shunichiro Ito, Kazuo Tanaka, Yoshiki Chujo
Summary: We synthesized new binuclear boron complexes based on pyrazine with ortho and para substitution patterns. The para-linked complexes showed a narrow energy gap between highest occupied and lowest unoccupied molecular orbitals, resulting in far-red to near-infrared emission properties. Meanwhile, the ortho-substituted complex exhibited orange emission. The theoretical study suggested that the para-substitution did not significantly perturb the characteristic HOMO distribution originating from pyrazine, unlike the ortho-substituted one.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Polymer Science
Chisa Takahara, Masashi Nakamura, Yuto Aoyama, Takumi Yanagihara, Shunichiro Ito, Kazuo Tanaka, Hiroaki Imoto, Kensuke Naka
Summary: Arsenic-containing conjugated polymers, with dithieno[3,2-b:2',3'-d]arsole as a typical monomer unit, have gained significant attention recently. However, the traditional polymer design for improved solubility often involves introducing long alkyl chains, which may lead to steric hindrance and distort the planarity of the polymer chain. To overcome this, a novel monomer with an alkoxyphenyl group substituted on the arsenic atom was developed. These polymers, using benzothiadiazole and benzoxadiazole monomers, exhibited high planarity and solubility, as well as near-infrared emissions.
Article
Polymer Science
Kazumasa Suenaga, Aoi Watanabe, Kazuo Tanaka, Yoshiki Chujo
Summary: The logical design and synthesis of a blue-luminescent film based on a conjugated polymer is demonstrated by utilizing aza-substituted FBKI. The aza-substituted FBKIs exhibit solid-state luminescent properties and wider energy gaps compared to the corresponding FBKIs. A conjugated homopolymer including azaFBKI as a repeating unit is successfully designed and obtained, which shows purely blue luminescence in film.
Article
Polymer Science
Masashi Nakamura, Momona Yamauchi, Masayuki Gon, Kazuo Tanaka
Summary: This study achieved efficient wavelength conversion from ultraviolet to near-infrared light by introducing pyrene into polymers, providing significant implications for the research of wavelength converting materials.
Review
Polymer Science
Kazuo Tanaka
Summary: A new method to control the electronic states of conjugated polymers without extending the pi-conjugated system was developed by aza-substitution of isolated frontier molecular orbitals (FMOs). This method efficiently and selectively lowers the energy level of FMOs, leading to the synthesis of materials with blue and near-infrared emitting properties.
Article
Polymer Science
Masayuki Gon, Misato Kanjo, Shunsuke Ohtani, Kazuo Tanaka, Yoshiki Chujo
Summary: This study demonstrated the synthesis of a new series of solid-state luminescent pi-conjugated polymers with tunable energy levels. These polymers exhibited intense luminescence in both solutions and films. By selectively perturbing the energy levels of the frontier molecular orbitals (FMOs) and utilizing condensed reagents in the azomethine bond formation reaction, the monomer structure and the perturbed FMOs could be determined.
Article
Chemistry, Physical
Junki Ochi, Takumi Yanagihara, Kazuo Tanaka, Yoshiki Chujo
Summary: We synthesized two types of regioisomers fused by a phenylnaphthalene ring with different connection points to the o-carborane scaffold. In this study, we investigated their photoluminescence properties and photochemical mechanisms in detail. Interestingly, despite having a common aromatic unit, they exhibited different photoluminescence characters in terms of wavelength and dual-emission, which were determined by the substitution position of aryl groups to o-carborane as indicated by variable-temperature photoluminescence measurements and quantum chemical calculations. It was further revealed that the relative position of the C-C bond of o-carborane and the aryl center played a crucial role in the photophysical events of aryl-o-carboranes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Shunya Tanaka, Daisuke Sakamaki, Naoki Haruta, Tohru Sato, Masayuki Gon, Kazuo Tanaka, Hideki Fujiwara
Summary: In this study, a novel double N,S-hetero[5]helicene composed of two benzo[b]phenothiazines was reported, which exhibited long-lived circularly polarized room-temperature phosphorescence. The intense and long-lived phosphorescence of the compound was explained by theoretical calculations. Optical resolution was successfully achieved, and the chiroptical properties of the compound were investigated. This compound represents a rare example of a purely-organic helicene that exhibits long-lived circularly polarized RTP from a non-aggregated state.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)