Article
Chemistry, Multidisciplinary
Lin Wang, Qiuhong Cheng, Aiyou Hao, Pengyao Xing
Summary: This study utilizes chiral deep eutectic solvents (DESs) to control supramolecular chirality and illustrates the structural basis for the fabrication of DES-based chiral materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hui Shen, Zhen Xu, Lingzheng Wang, Ying-Zi Han, Xianhu Liu, Sami Malola, Boon K. Teo, Hannu Hakkinen, Nanfeng Zheng
Summary: The study introduces a novel synthetic strategy to successfully synthesize tertiary chiral nanostructures with 100% optical purity. These structures consist of tri-metallic superatoms with inherent chirality and fair stability, driven by C-H...F interaction during self-assembly.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xiao Xiao, Qian Cheng, Si Tong Bao, Zexin Jin, Shantao Sun, Haoyu Jiang, Michael L. Steigerwald, Colin Nuckolls
Summary: We demonstrate the access to single-handed helicene nanoribbons by utilizing a [6]helicene building block to induce diastereoselective, photochemical formation of [5]helicene units. The synthesized nanoribbons are the longest, optically active helicene backbones to date and exhibit the transfer of stereochemical information from one helicene unit to another.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Shixin Fa, Keisuke Adachi, Yuuya Nagata, Kouichi Egami, Kenichi Kato, Tomoki Ogoshi
Summary: Regulating the chirality of macrocyclic host molecules and supramolecular assemblies is crucial for governing their properties, and pre-regulation of building blocks' chirality in pillar[5]arene-based chiral nanotube formation has been shown to be more efficient than post-regulation strategies.
Article
Chemistry, Physical
Yuxia Zhang, Zhongxing Geng, Yu Zhang, Zhaoran Xu, Hang Li, Yixiang Cheng, Yiwu Quan
Summary: The study synthesized three achiral pyrene derivatives and found that only the chiral co-assembly could form regular and orderly helical nanofibers, emitting a strong deep blue circularly polarized luminescence signal.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Wenyao Zhang, Jie Zhao, Dong Yang, Boyang Li, Yang Feng, Yue Wang, Xiaoyan Zheng, Xiao-Juan Yang, Biao Wu
Summary: This study presents the chiral induction and memory effect in an anion-coordination-driven tetrahedral cage. The induced chirality can be retained for a certain period even after replacing the chiral guests with achiral ones. The retention time of induced chirality can be controlled by using different achiral guests.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Zhuoer Wang, Aiyou Hao, Pengyao Xing
Summary: The researchers successfully realized chiroptical properties in the near-infrared (NIR) region using a charge-transfer strategy and applied it to photothermal agents. They self-assembled pyrene-conjugated amino acid derivatives into helical structures with supramolecular tilt chirality. By manipulating the amino acid domains, they achieved chiroptical activity evolution in the NIR region and controlled the photothermal performance using circularly polarized NIR light.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Wei-Dan Si, Kai Sheng, Chengkai Zhang, Zhi Wang, Shan-Shan Zhang, Jian-Min Dou, Lei Feng, Zhi-Yong Gao, Chen-Ho Tung, Di Sun
Summary: This study reports the spontaneous assembly of unique P- and M-single stranded helical superstructures from R- and S-Au8c individual nanoclusters, respectively, using chiral BINAP and hydrophilic o-HMBA as ligands. The chirality of the nanoclusters is derived from the homochiral ligands and the inherently chiral Au-8 metallic kernel. The helical superstructures are formed through O-H···O interactions between (HCO3-)(2) dimers and achiral o-HMBA(-) ligands. This work provides an effective strategy to construct cluster-based helical superstructures at the atomic level and offers experimental evidence for understanding the formation mechanism of helical superstructures.
Article
Chemistry, Organic
Xinyue Tian, Yao Xiao, Shuoyingjie Wang, Guanghua Liu, Wenhao Zhang, Laiyun Zhou, Jianye Gong, Xuejin Zhang, Xiang Li, He Meng, Jianguo Wang, Gaole Dai, Qing Wang
Summary: Incorporating two pyrrole subunits at the bay positions of perylene-diimide, PDI-2N, with a bowl depth of 1.52 angstrom, was successfully synthesized via one step Buchwald-Hartwig reaction. Despite the electron-rich pyrrole embedding, the radical anion and dianion of PDI-2N were easily prepared and investigated experimentally and theoretically. Furthermore, PDI-2N crystallized in different manners under distinct conditions, forming tubular crystals with infinite two-directional columnar stacking under DMF conditions. This discovery presents a promising bowl-shaped PDI derivative for organoelectronics.
Article
Chemistry, Organic
Manuel A. Martinez, Daniel Aranda, Enrique Orti, Juan Arago, Luis Sanchez
Summary: The self-assembling features of amphiphilic N-annulated perylene bisimides (N-PBIs) 1-4 in water were investigated experimentally and theoretically. The hydrophilic/hydrophobic ratio, determined by the oligo(ethylene) glycol (OEG) chains in the monomers, plays a significant role in the enthalpy of self-assembly. Molecular dynamic simulations revealed the influence of the initial arrangement of hydrophilic side chains and water-side chain interactions on the enthalpy contribution and overall stability of the aggregated species in water.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Dorian Sonet, Matteo Cayla, Raphael Mereau, Estelle Morvan, Aline Lacoudre, Nicolas Vanthuyne, Muriel Albalat, Dario M. Bassani, Antoine Scalabre, Emilie Pouget, Brigitte Bibal
Summary: The effects of introducing chiral trifluoromethyl alcohol groups on the physical properties and reactivity of 9,10-diphenylanthracenes were investigated. It was found that the position and orientation of the -CH(OH)CF3 groups in the molecules depend on the relative and absolute configurations of each stereoisomer. The study demonstrated that stereochemistry governs the molecular organization in crystals and impacts the reaction products, as well as modulates the chiroptical properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Manuel Weh, Jessica Ruehe, Benedikt Herbert, Ana-Maria Krause, Frank Wuerthner
Summary: The deracemization process of a racemic mixture of chiral molecules into enantioenriched compounds is achieved by an inherently chiral perylene bisimide cyclophane, which can transform [5]-helicene into an enantioenriched mixture with a high enantiomeric excess. The macrocyclic supramolecular host shows strong and enantioselective binding towards homochiral carbohelicenes, suggesting potential applications in template-catalyzed deracemization processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Meng Sun, Shiqiao Peng, Lei Nie, Yunqing Zou, Li Yang, Laiben Gao, Xiaoqiu Dou, Changli Zhao, Chuanliang Feng
Summary: By transferring chirality from molecular chirality to achiral polymers, a 3D chiral catalytic microenvironment has been constructed, showing significantly enhanced catalytic activity and efficient recyclability, which can improve the catalytic efficiency of lipase.
Article
Chemistry, Multidisciplinary
Fenghua Zhang, Zongze Zhang, Rongjuan Liu, Jingjing Wei, Zhijie Yang
Summary: It is shown that aqueous dispersions of negatively charged inorganic nanoparticles can induce the chiral assembly of organic radical cations at the liquid-liquid interface, resulting in stable droplets covered by inorganic/organic chiral nanocomposites. Transfer of chirality from chiral organic monomers to the nanoparticle assemblies is observed. Surprisingly, opposite handedness between molecular assemblies and nanoparticle assemblies is determined. Moreover, the functionalities of these chiral droplets can be further engineered through mixing or merging, enabling the production of fluorescent emissive-tunable, magnetic, as well as magnetofluorescent dual-functional droplets.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Yuxia Zhang, Wenting Yu, Hang Li, Wenhua Zheng, Yixiang Cheng
Summary: Circularly polarized luminescence (CPL) has gained significant interest for its potential applications in chiral photonic techniques and optoelectronic materials science. The dissymmetry factor (g(em)) plays an essential role in evaluating the properties of CPL-active materials. Recent studies have shown that chiral supramolecular co-assemblies can effectively enhance the g(em) value through the ordered helical superstructure of chiral building blocks. The chirality transfer and induction mechanism in this assembly process promote the amplification effect of induced CPL in achiral dyes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jorge S. Valera, Hironari Arima, Cristina Naranjo, Takuho Saito, Natsuki Suda, Rafael Gomez, Shiki Yagai, Luis Sanchez
Summary: The hierarchical self-assembly of scissor-shaped azobenzene dyads leads to the formation of discrete nanotoroids in solution, which further organize into well-defined 2D porous networks on a graphite surface. The steric demand of peripheral aliphatic units controls the stackability of nanotoroids in solution. Additionally, reversible dissociation and reconstruction of nanotoroids can be achieved through UV and visible light photoirradiation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Keigo Tashiro, Takuho Saito, Hironari Arima, Natsuki Suda, Balaraman Vedhanarayanan, Shiki Yagai
Summary: Chemists have constructed sophisticated artificial nanostructured systems through self-assembly, including scissor-shaped photochromic dyads that hierarchically self-assemble into discrete nanostructures with photoresponsive properties. These nanostructures, such as azobenzene dyads, can be dissociated and reorganized through the photoisomerization of azobenzene units, enabling controllable and adjustable structures.
Article
Chemistry, Physical
Fabien Silly, Maika Kawaura, Takumi Aizawa, Hayato Ouchi, Shiki Yagai
Summary: The self-assembled structures of a hydrogen-bonding oligo(thiophene) molecule functionalized with a barbiturate unit were investigated at different hierarchical levels. It was found that two distinct molecular self-assembly pathways exist, leading to the formation of rodlike and helical nanofibers.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Maika Kawaura, Takumi Aizawa, Sho Takahashi, Hiroshi Miyasaka, Hikaru Sotome, Shiki Yagai
Summary: The study demonstrates that barbiturate-based molecules can form nanostructures through supramolecular polymerization under specific conditions, enhancing the emission efficiency. Additionally, the positional difference in regioisomers also influences the interchain association of supramolecular polymers, resulting in different luminescent soft materials.
Article
Chemistry, Multidisciplinary
Natsuki Suda, Takuho Saito, Hironari Arima, Shiki Yagai
Summary: Recent advances in supramolecularly engineered dye aggregates have allowed for the design and control of simple one-dimensional structures and closed structures. In this study, a new dyad was introduced that can form nanotoroids, nanotubes, or 1D fibers depending on the conditions. This is the first successful example of light-induced modulation of supramolecular polymorphism to produce distinctly nanostructured aggregates under isothermal conditions.
Article
Chemistry, Multidisciplinary
Natsuki Suda, Hironari Arima, Takuho Saito, Takumi Aizawa, Shiki Yagai
Summary: A scissor-shaped foldable diphenylanthracene dyad has been synthesized to self-assemble into elongated thin nanofibers in a nonpolar solvent, exhibiting intense blue emission. Efficient gelation was observed at millimolar concentration while maintaining the emission property in the gel state.
Article
Chemistry, Multidisciplinary
Sho Takahashi, Shiki Yagai
Summary: This study demonstrates an example of thermodynamically controlled random supramolecular copolymerization. By forming six-membered hydrogen-bonded rosette intermediates, the random copolymerization of two monomers with distinct molecular structures is achieved. The experimental results reveal the homopolymerization of one monomer in the high-temperature region and the incorporation of the other monomer in the medium-temperature region to form supramolecular copolymers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Ryohei Sato, Atsuo Utagawa, Koji Fushimi, Feng Li, Takuya Isono, Kenji Tajima, Toshifumi Satoh, Shin-ichiro Sato, Hiroshi Hirata, Yoshihiro Kikkawa, Takuya Yamamoto
Summary: The redox behaviors of macrocyclic molecules with an entirely pi-conjugated system were investigated in this study. Cyclic P3HT with different degrees of polymerization (DPn) were synthesized, and its unique redox behaviors were compared with linear P3HT. Cyclic P3HT showed a decrease in HOMO level and greater stability during cyclic voltammetry measurement, indicating stronger dicationic properties due to polaron-polaron interactions.
Article
Chemistry, Multidisciplinary
Suyi Liu, Yasuo Norikane, Seiji Tsuzuki, Shotaro Ito, Yoshihiro Kikkawa
Summary: The two-dimensional structures of Cu(II)-coordinated curcumin derivatives were observed using scanning tunneling microscopy. Cu(II) coordination led to the formation of dimerized structures, which differed from the original curcumin derivatives. The appearance and disappearance of the two-dimensional structure modulation were dependent on the number of alkyl chain substituents. Furthermore, the odd-even effect was found to be maintained before and after Cu(II) coordination.
Article
Chemistry, Physical
Suyi Liu, Yasuo Norikane, Seiji Tsuzuki, Shotaro Ito, Yoshihiro Kikkawa
Summary: This study focuses on the two-dimensional self-assemblies of curcumin derivatives. The effects of the number, length, and substitution of the alkyl chains on the 2D structures of curcumin derivatives were investigated. It was found that curcumin derivatives with methoxy and alkoxy chain groups exhibit different linear structures, while those with four alkoxy chains do not have interdigitation structures. Furthermore, the alkyl chain length was found to have an odd-even effect on the structure of bisdemethoxycurcumin derivatives.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Yoshihiro Kikkawa, Seiji Tsuzuki
Summary: Understanding the interactions between adsorbates and substrates is crucial in various scientific fields. This study used density functional theory calculations to examine the interactions of n-alkanes and n-perfluoroalkanes with circumcoronene. The results showed that the interactions of n-perfluoroalkanes were weaker than those of n-alkanes due to steric repulsion and a mismatch in equilibrium distance. The adsorption energies of n-perfluorohexane and n-hexane were significantly different, indicating the importance of these interactions in stabilizing the adsorbed molecules.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Yoshihiro Kikkawa, Mayumi Nagasaki, Yasuo Norikane
Summary: The correlation between molecular arrangement and physical properties of organic compounds was studied using azobenzene derivatives. The effects of methyl substitution and alkyl chain length on the 2D molecular arrangements were revealed.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Chi Feng, Tomohiro Seki, Shunichi Sakamoto, Toshiyuki Sasaki, Satoshi Takamizawa, Hajime Ito
Summary: This study discovered a reversible multi-stage shape-changing effect in a molecular crystal, where the shape changes and luminescence-color changes were induced by multi-step thermal phase transitions. The findings provide new strategies for imparting additional functionalities to known shape-memory materials.
Article
Chemistry, Multidisciplinary
Takumi Aizawa, Maika Kawaura, Takashi Kajitani, Kowit Hengphasatporn, Yasuteru Shigeta, Shiki Yagai
Summary: This study reports the self-assembly of 2-thiobarbituric acid-functionalized naphthalene dye into crystalline fibers, which exhibit different material properties compared to the previously reported oxo-barbituric acid derivative that forms curved supramolecular polymers. Detailed analysis using H-1-NMR, DFT calculation, and X-ray diffraction reveals that the crystalline fiber is formed through a tape-like hydrogen-bonding pattern due to the weaker hydrogen-bond-acceptor ability of the thiocarbonyl group.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Sougata Datta, Sho Takahashi, Shiki Yagai
Summary: Recently, supramolecular polymers (SPs) have gained attention as a class of materials that can overcome the potential environmental problems of conventional polymeric materials. The development of various supramolecular polymers is important not only for their direct application as materials but also because their unique polymerization processes and dynamic properties have a profound influence on the development of polymeric and small-molecule-based functional materials. By limiting the dimensionality of molecular assemblies to one dimension, essential aspects of self-assembly and self-organization can be discovered. Curved supramolecular polymers (CSPs) have been studied to understand the major features of polymer chains when intrinsic structural order generates curvature. The use of one-dimensional stacked supramolecular polymers allows for free control of structure at the single-polymer-chain level.
ACCOUNTS OF MATERIALS RESEARCH
(2022)