Article
Chemistry, Multidisciplinary
Zhe Liu, Wenru Song, Shaojie Yang, Chengshan Yuan, Zitong Liu, Hao-Li Zhang, Xiangfeng Shao
Summary: In this study, waterwheel-like three-dimensional polycycles 4a/4b were synthesized by fusing bowl-shaped trichalcogenasumanenes onto branches of triptycene. The results showed that 4a/4b exhibited strong UV-Vis absorbance and excited state absorption in the NIR-II window. They also formed stable host-guest complexes with fullerene C-60/C-70, with higher affinity towards C-70.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Engineering, Electrical & Electronic
Tao An, Jia Miao, Ximei Wu, Tianbao Xie
Summary: The paper proposes a ternary organic photomultiplier detector doped with C-70:C-60 double electron traps in the P3HT:PTB7:PC61BM photoactive layer, which significantly improves the photomultiplier efficiency and external quantum efficiency of the device.
SENSORS AND ACTUATORS A-PHYSICAL
(2021)
Article
Biochemistry & Molecular Biology
Subbareddy Mekapothula, A. D. Dinga Wonanke, Matthew A. Addicoat, David J. Boocock, John D. Wallis, Gareth W. V. Cave
Summary: A silica-bound C-butylpyrogallol[4]arene chromatographic stationary phase was prepared and characterized, showing size-selective molecular recognition properties for C-60 and C-70 fullerenes. The presence of toluene in the mobile phase was found to play an important role in achieving symmetrical peaks in flash column chromatography, demonstrating the effectiveness of the new stationary phase in separating fullerene mixtures.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Biochemistry & Molecular Biology
Ivan V. Mikheev, Madina M. Sozarukova, Dmitry Yu. Izmailov, Ivan E. Kareev, Elena V. Proskurnina, Mikhail A. Proskurnin
Summary: The antioxidant potential of aqueous fullerene dispersions (AFD) of non-functionalized C-60, C-70, and Gd@C-82 endofullerene was evaluated through chemiluminescence measurements and mathematical modeling of long-term kinetics data. The study found that the antioxidant capacity of AFDs increased in the order Gd@C-82 < C-70 < C-60, with Gd@C-82 showing actual antioxidant action 300-fold higher than quenching constants.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Physical
Li Wang, Yan-Li Liu, Sheng-Hui Chen, De He, Quan-Jiang Li, Mei-Shan Wang
Summary: This study investigated the effects of different stacking modes between corannulene and fullerene on the stability and NLO properties of the composite materials. The concave-convex interaction was found to be stronger, stabilizing the CT complex more effectively, while the convex-convex interaction was more likely to cause intermolecular CT. The packing design with double convex-convex interactions exhibited the largest linear optical response and third-order NLO response.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Medicinal
Marta Queizan, Marta Sanchez-Lozano, Marcos Mandado, Jose M. Hermida-Ramon
Summary: By combining multiple hydrogen bonds and anion-pi interactions, neutral metal-free receptors are capable of recognizing anions in highly polar solvents. An aromatic molecular tweezer functionalized with azo groups efficiently captures anions in water, exhibiting high thermodynamic stability and strong bonding within the system. Theoretical and first-principles quantum methods confirm the stability of the anion-tweezer complex over time, with the anion consistently located within the cavity of the tweezer.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2021)
Article
Nanoscience & Nanotechnology
Serhii Vasylevskyi, Guillaume Raffy, Stefan Salentinig, Andre Del Guerzo, Katharina M. Fromm, Dario M. Bassani
Summary: An anthracene-based Ni-MOF material capable of adsorbing C60 and C70 was reported, with fullerenes showing homogeneous distribution in single crystals under confocal fluorescence and Raman microscopy. Efficient energy transfer from 1 to fullerenes and stronger binding between 1 and C70 than C60 were observed, providing a basis for the selective retention of C70 in liquid chromatography columns packed with 1.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Nanoscience & Nanotechnology
Gefei Niu, Jianqun Geng, Xingyue Wang, Xiaotian Yang, Wei Xiong, Hui Zhang, Zilin Ruan, Yong Zhang, Lei Gao, Jianchen Lu, Jinming Cai
Summary: Two-dimensional supramolecular self-assembly architectures are crucial for nanotechnology and modern organic chemistry, and studying these processes on surfaces is essential for controlling supramolecular designs. This research examines the self-assembly monolayer architectures of C-60 and C-70 molecules on a CuSe monolayer with periodic nanopores, providing insights for surface template chemistry. Through low-temperature scanning tunneling microscopy/spectroscopy and density functional theory calculations, the study investigates the adsorption configurations and electronic properties of these molecules. The results reveal that the molecules above the nanopores fall into them, while those on the CuSe surface show well-defined self-assembly with various adsorption configurations, leading to slight differences in the lowest unoccupied molecular orbitals and characteristic peaks.
Article
Chemistry, Multidisciplinary
Jia-Qi Wang, Ying Han, Chuan-Feng Chen
Summary: A new class of macrocyclic arenes, 3,6-fluoren[5]arenes, were successfully synthesized in good yields and could form stable complexes with fullerenes C-60 and C-70 due to their symmetric pentagon structures with big and rich-electron cavities.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Lu'an Guo, Yitao Wang, Dogan Kaya, Zhiming Wang, Min Zhang, Quanmin Guo
Summary: Researchers successfully built a C-60-C-70 organic molecular heterojunction on the HOPG surface using layer-by-layer growth method. C-70 molecules assemble into a close-packed second layer matched to the underlying C-60 layer, showcasing unique physical properties and functionality.
APPLIED SURFACE SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Tomoaki Tanase, Kanako Nakamae, Yasutaka Kitagawa, Takayuki Nakajima
Summary: Reactions of Pd-8 strings supported by meso-dpmppm ligands resulted in the exclusive formation of unprecedented metal-chain-wired C-60 bucky balls, with C-60 trapped in the central Pd-Pd junction. Similar reactions were applied for trapping a C-70 fullerene. These results provide useful information for developing dimensionally and chirality controlled metal-carbon nanocomposite materials.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Junning Kou, Qi Wu, Dongxu Cui, Yun Geng, Kunhao Zhang, Min Zhang, Hongying Zang, Xinlong Wang, Zhongmin Su, Chunyi Sun
Summary: The article reports the successful encapsulation and selective binding of C-70 fullerene by two new pairs of chiral porous aromatic cages. The occurrence of chiral induction is confirmed through experimental evidence. The study reveals the influence of electrostatic effects and substituents on fullerene encapsulation and selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Desmond MacLeod Carey, Alvaro Munoz-Castro
Summary: A new structure for spherical fullerene has been evaluated by replacing every C-vertex from C-60 with sixty phenylene rings. Density functional theory calculations confirm stability and properties, predicting a related C-70 counterpart and nano-onions incorporating C-60 and C-70. These structures exhibit increased redox potentials and larger pi-surface area compared to C-60 and C-70, which are relevant for photovoltaic applications.
Article
Chemistry, Multidisciplinary
E. N. Ovchenkova, N. G. Bichan, M. S. Gruzdev, A. A. Ksenofontov, F. E. Gostev, I. V. Shelaev, V. A. Nadtochenko, T. N. Lomova
Summary: Two supramolecular cobalt(ii) porphyrin-fullerene systems were successfully synthesized and characterized via axial coordination, showing potential photoelectrical properties. The data obtained are crucial for further photoelectrochemical study and the development of photovoltaic devices.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
A. Bautista Hernandez, Wilfredo Ibarra Hernandez, F. Severiano, E. Garcia Hernandez, E. Chigo Anota, M. Salazar Villanueva
Summary: The structural and electronic properties of Zn-m@C-60 and Zn-m@C-70 endohedral metallofullerenes (m = 1-5) were investigated using DFT calculations. Despite having higher binding energies, these endohedral metallofullerenes are energetically stable. Encapsulating Zn-4 and Zn-5 clusters inside C-60 and C-70 fullerenes leads to structural transformations and electronic changes, improving their absorption of visible and ultraviolet light. These properties have potential applications in areas such as heavy metal encapsulation, electronic device design, gas sensors, and solar cells.
SURFACES AND INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Shusaku Ukai, Aiko Takamatsu, Masaki Nobuoka, Yusuke Tsutsui, Norihito Fukui, Soichiro Ogi, Shu Seki, Shigehiro Yamaguchi, Hiroshi Shinokubo
Summary: In this study, a supramolecular polymer consisting of an antiaromatic π-system as the monomer was successfully constructed. The resulting supramolecular polymer exhibited higher charge mobility due to the persistence of the conducting pathway against thermal perturbation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Asahi Takiguchi, Erika Sakakibara, Hiroshi Sugimoto, Osami Shoji, Hiroshi Shinokubo
Summary: Using artificial hemes to reconstruct natural heme proteins enhances their bioactivity. Researchers synthesized metal 5-oxaporphyrinium cations and successfully incorporated cobalt 5-oxaporphyrinium cation into heme-acquisition protein secreted by Pseudomonas aeruginosa. The hypothesis is that the oxaporphyrinium cation binds strongly to the HasA-specific outer membrane receptor, preventing heme acquisition. In fact, the reconstructed HasA inhibits the growth of Pseudomonas aeruginosa and multidrug-resistant P. aeruginosa.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Masaki Kato, Norihito Fukui, Hiroshi Shinokubo
Summary: A new molecule with a double-helicene-like structure was successfully synthesized via an intermediate, and its helical inversion and absorption characteristics were analyzed by theoretical calculations.
Article
Chemistry, Multidisciplinary
Atsumi Yagi, Naoya Okada, Norihito Fukui, Hisaaki Tanaka, Takuji Hatakeyama, Hiroshi Shinokubo
Summary: The synthesis of Pd(II) and Cu(II) 10-azacorroles with a meso-NH group has been achieved through thermal extrusion, and the oxidation of Cu(II) 10-azacorrole complex resulted in another type of copper 10-azacorrole with an imine moiety. The structural, magnetic, and electrochemical properties of these compounds were investigated to reveal the nature of the two types of copper 10-azacorroles.
Article
Chemistry, Multidisciplinary
Takahiro Sakurai, Yuya Hiraoka, Hisaaki Tanaka, Yoshihiro Miyake, Norihito Fukui, Hiroshi Shinokubo
Summary: Ni-II 3,7,13,17-tetrapyridyl-5,15-diazaporphyrin acts as a double tridentate ligand for Pd-II ions, leading to the formation of a pincer-type bispalladium complex. The bispalladium complex exhibits excellent electron accepting ability and reversible redox properties due to the coordination of the two cationic Pd-II centers to the meso-nitrogen atoms. One- and two-electron reduction species of the bispalladium complex have been isolated, characterized, and confirmed to have a 20 pi antiaromatic nature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Masaki Kato, Jinseok Kim, Juwon Oh, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo
Summary: The relationship between the electronic structure and the arrangement of constituent elements in pi-conjugated molecules is discussed. The synthesis and properties of three conjugated hydrocarbons with NIR absorption and emission are described. The effect of pi-extension on achieving a narrow HOMO-LUMO gap with negligible antiaromaticity and diradical character is also discussed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Shiori Itabuchi, Ryo Nozawa, Takuya Yoshida, Norihito Fukui, Hiroshi Shinokubo
Summary: In this study, a novel norcorrole Ni(II) complex with distinct antiaromatic character was synthesized. The antiaromatic nature of the complex was evaluated using experimental and computational methods, and the differences in molecular structure and crystal packing arrangement were revealed by X-ray diffraction analysis.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2023)
Article
Chemistry, Multidisciplinary
Shiho Mori, Takahiro Sakurai, Tsubasa Nishimura, Norihito Fukui, Yoshihiro Miyake, Hiroshi Shinokubo
Summary: We synthesized a freebase diphenyl diazaporphyrin and its complexes with Ni(II), Cu(II), Pd(II), and Pt(II). These molecules form a one-dimensional pi-stacking array in the solid state. The crystal packing arrangement is dominated by four-fold intermolecular hydrogen bonding interactions between the meso-nitrogen atom of the diazaporphyrin core and the ortho-hydrogen atom of the phenyl substituent. This study demonstrates the potential of using meso-nitrogen atoms in diazaporphyrins as hydrogen bonding acceptors for constructing supramolecular assemblies.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2023)
Article
Chemistry, Organic
Mai Odajima, Norihito Fukui, Hiroshi Shinokubo
Summary: This study reports the synthesis and properties of a dinaphthooxepine bisimide (DNOBI), a nonplanar perylene bisimide (PBI) analogue with an inserted oxygen atom. DNOBI smoothly underwent an oxygen-extrusion reaction upon electron injection at room temperature, yielding PBI in good yield. Studies on the reaction mechanism suggest that the isomerization of DNOBI to dinaphthooxanorcaradiene bisimide upon the injection of two electrons is a key step in inducing the oxygen-extrusion reaction.
Article
Chemistry, Multidisciplinary
Keita Tajima, Kyohei Matsuo, Hiroko Yamada, Norihito Fukui, Hiroshi Shinokubo
Summary: In this study, a strongly electron-accepting pi-system, diazazethrene bisimide (DAZBI), was developed by incorporating imide substituents and imine-type nitrogen atoms into zethrene. DAZBI exhibited a low-lying LUMO (-4.3 eV vs. vacuum) and was readily reduced to the corresponding dihydro species by a weak reductant, l-ascorbic acid. Injection of two electrons into DAZBI resulted in the formation of a stable dianion with intense red fluorescence. Additionally, a DAZBI dimer was synthesized, which effectively accommodated four electrons upon electron injection.
Article
Chemistry, Physical
Sara Suzuki, Soni Aman Govind, Kosuke Imamura, Hideki Yorimitsu, Hiroshi Shinokubo, Masahiro Higashi, Hirofumi Sato
Summary: The radical cyclization reaction in aqueous environment by Yorimitsu et al. was reexamined using the RISM-SCF-cSED method, a hybrid approach combining quantum chemistry and statistical mechanics for molecular liquids. The difference in barrier height between the forward reaction from the intermediate E-rot, the cyclization step, and the backward reaction is crucial for the reaction yield. By considering the effect of hydrogen bonding through the RISM theory, it was found that the barrier height for the forward reaction is lower, particularly in water. In other words, accounting for microscopic solvation effects clearly elucidates the disparity between water and DMSO solvents, explaining the significant acceleration of the reaction in the aqueous environment.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Chemistry, Physical
Zeming Wang, Rui Jing, Yang Li, Di Song, Yan Wan, Norihito Fukui, Hiroshi Shinokubo, Zhuoran Kuang, Andong Xia
Summary: Disulfide bridges in proteins exhibit excellent photostability, while the cleavage and reforming dynamics of disulfide bonds in aromatic compounds are affected by the rigid chemical structure. In this study, the effect of disulfide modification on the excited-state deactivation mechanism was investigated using a model compound with a disulfide five-membered-ring structure. It was found that the excellent photostability was achieved through ultrafast excited-state quenching induced by the S-S stretching, instead of the cleavage of the disulfide bond.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Organic
Yoshihiro Takeo, Junichiro Hirano, Norihito Fukui, Hiroshi Shinokubo
Summary: We investigated the chemical and physical properties of internally functionalized DBC derivatives. These molecules exhibit chiral double-helicene-like structures that are configurationally stable at ambient temperatures. The conformational change in the excited state is controlled by the internal substituents, thereby modulating the emission intensity. Notably, the DBC derivative with a methylenedioxy unit undergoes aromatization through elimination of the internal substituent upon photoexcitation, resulting in the formation of DBC.
Article
Chemistry, Organic
Yoshihiro Takeo, Junichiro Hirano, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo
Summary: This study compares a bowl-shaped aromatic hydrocarbon with internal methoxy groups to its derivatives with hydrogen, methyl, and anisyl groups. The methoxy-substituted derivative exhibits enhanced electron-accepting properties and changes in absorption properties. The results provide insights into the structure-property relationships in graphene oxide and advanced fullerene receptors.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Asahi Takiguchi, Naoto Inai, Seongsoo Kang, Masaya Hagai, Seokwon Lee, Takeshi Yanai, Dongho Kim, Hiroshi Shinokubo
Summary: Thionium-ion embedded aromatic porphyrinoids were synthesised and their photophysical analysis and theoretical calculations revealed that the vibrational mode of the sulphur atom is responsible for the ultrafast quenching of the excited state.
CHEMICAL COMMUNICATIONS
(2022)