Article
Chemistry, Organic
Damian E. Yerien, Jessica Groppi, Al Postigo, Alberto Credi, Romina S. Conde, Massimo Baroncini, Sebastian Barata-Vallejo
Summary: Modified crown ethers are essential in supramolecular chemistry, and have applications in various fields such as phase transfer catalysis, metal extraction, smart materials, and molecular machines. In this study, a one-pot highly selective photocatalytic fluoroalkylation protocol was developed for the mono-functionalization of benzo substituted crown ethers. With broad applicability and high yield, this method allows for the late-stage functionalization of various aromatic crown ethers, including those involved in mechanically interlocked molecules.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yoko Sakata, Ryosuke Nakamura, Toshihiro Hibi, Shigehisa Akine
Summary: Switching between formation and dissociation of rotaxanes is important for controlling the function of rotaxane-based materials. We developed a convenient strategy called accelerator addition to make a static rotaxane dynamic without affecting the chemical structure. By complexing [PdL2](2+) (L=2,3-diaminotriptycene) with 27C9, a metallorotaxane was quantitatively generated, allowing for tuning of formation and dissociation speed. Addition of Br- accelerated rotaxane formation by 27 times, while Cs+ accelerated dissociation, forming the free axle [PdL2](2+) and the 27C9-Cs+ complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Aleksandra Sarwa, Agata Bialonska, Mateusz Garbicz, Bartosz Szyszko
Summary: Depending on the size and basicity of the anion, the self-assembly of 2,5-diformylpyrrole, tris(2-aminoethyl)amine, and silver(I) resulted in new cascade complexes or plenates, which are cryptates incorporating Ag-n(n+) clusters. The nature of the product was determined by the counterion and its formation was driven by either cascade anion binding or argentophilic interactions stabilizing the cluster within the cavity. The reaction of plenates with tetrabutylammonium halides led to the protonation-coupled replacement of the Ag-3(3+) with anion(s), forming cascade cryptates.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Kajetan Dabrowa, Magdalena Ceborska, Janusz Jurczak
Summary: This paper presents a comparative analysis of the solid state structures of three well-resolved hydrates of macrocyclic host molecules 1a, 1b, and 2, revealing that despite different chemical structures, they crystallize as isostructural tetrahydrates in the same space group. The crystals of these hosts exhibit identical hydrogen bond motifs resulting in an almost identical unusual octameric water cluster, with host 2 providing the most suitable environment for accommodating this type of water cluster.
Article
Chemistry, Organic
Yanyan Tan, Shaowu Pan, Shilong Zhang, Lin Fang, Feichun Zhang, Yuanyuan Zhang, Lasheng Jiang
Summary: Here, we report the syntheses of two new crown-ether-based cryptands and their complexation behaviors with neutral organic molecules. We found that one of the cryptands showed excellent complexation ability with G2, with a high association constant of 2.5x10(5) M-1.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tomoki Ogoshi, Miyu Yoshiki, Takahiro Kakuta, Tada-aki Yamagishi, Motohiro Mizuno
Summary: Polypseudorotaxanes were successfully synthesized using pillar[5]arene rings and polyamide chains via interfacial polymerization of diamines and dicarbonyl chlorides in the presence of pillar[5]arene. The length of dicarbonyl chloride and the association constants of dicarbonyl chloride-pillar[5]arene complexes were crucial factors in achieving polypseudorotaxanes with a high cover ratio of pillar[5]arene rings.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Maxime Gauthier, Frederic Coutrot
Summary: This study synthesized new pH-sensitive [2]rotaxane molecular shuttles and found that the Weinreb amide was not a suitable secondary molecular station for DB24C8, while the ketone was successfully used for this purpose.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Emily P. Bacher, Kevin J. Koh, Antonio J. Lepore, Allen G. Oliver, Olaf Wiest, Brandon L. Ashfeld
Summary: A phosphorus(III)-mediated dearomatization of ortho-substituted dianiline squaraine dyes led to the formation of exotic benzofuranone and oxindole scaffolds with a linear side chain comprised of an enol, a phosphorus ylide, and 2,4-disubstituted aniline. Mechanistic evaluation revealed a significant dependence on the acidity of the aniline ortho substituent, with the rearrangement adducts reverting back to the parent squaraine in the presence of a Bronsted acid.
Article
Chemistry, Organic
Yoichi Habata, Yuka Matsumoto, Hiroki Horita, Mari Ikeda, Shunsuke Kuwahara
Summary: A flexible cylindrical cryptand (1b) with two m-phenylene-26-crown-8 ethers has been found to have versatile complexing properties with respect to tetravalent cationic guests despite their differences in length and shape, according to diffusion-ordered spectroscopy nuclear magnetic resonance (NMR) and titration experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
James H. May, Jeff M. Van Raden, Ruth L. Maust, Lev N. Zakharov, Ramesh Jasti
Summary: In this study, a series of mechanically interlocked carbon nanostructures were synthesized using an active-template method. By catalyzing the reactions between a [n]cycloparaphenylene precursor macrocycle and metal ions, fully pi-conjugated catenanes and a [3]rotaxane were obtained. The developed synthetic method of mechanically interlocked carbon nanostructures can contribute to the understanding of the implications of mechanical bonding and provide insights into the structure-property relationships.
Editorial Material
Chemistry, Multidisciplinary
Daehyun Ahn, Nowshin Kabir, Thirumurugan Prakasam, Ali Trabolsi
Summary: The development of analytical tools over the past three decades has enabled the study of increasingly complex mechanically inter-locked molecules. The first synthesis of a [2]catenane by Edel Wasserman in 1960 was controversial due to the lack of experimental evidence. Recently, Leigh et al. re-examined this pioneering synthesis using modern techniques, confirming its structure in the Journal of the American Chemical Society.
Article
Chemistry, Multidisciplinary
Volodymyr Dudko, Katharina Ottermann, Sabine Rosenfeldt, Georg Papastavrou, Josef Breu
Summary: The study successfully extended repulsive osmotic delamination to polar and aprotic organic solvents by exerting pressure through the formation of complexation. Complete delamination was achieved in water-free solvents through this process.
Article
Chemistry, Inorganic & Nuclear
Caiyun Liu, Chang Gao, Amir Said, Huihui Niu, Dexin Wang, Chen-Ho Tung, Yifeng Wang
Summary: Catenane, rotaxane, and pseudorotaxane molecules based on a cyclic titanium oxide cluster and cyclic/linear alkylammonium cations were synthesized and shown to remain intact in acidic water, promising for assembling inorganic-organic hybrid supramolecular structures in water.
INORGANIC CHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
Yuki Ohishi, Kohei Nishioki, Yuta Miyaoka, Keita Serizawa, Souma Sugawara, Koichiro Hayashi, Daichi Inoue, Munetaka Iwamura, Satoru Yokoyama, Junya Chiba, Masahiko Inouye
Summary: A versatile synthetic method is established for [5]rotaxane-type fluorescence dyes by employing a cooperative capture strategy. These [5]rotaxanes show high emission efficiencies in water and even in the solid state and exhibit photostability and chemical stability, demonstrating the high applicability of [5]rotaxane-type fluorescence dyes for a variety of emitting materials.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Grace Turner, Andrew Docker, Paul D. Beer
Summary: A novel halogen bonding (XB) motif has been successfully incorporated into a [2]rotaxane using a discrete chloride anion template directed clipping methodology. Anion titration experiments show that the interlocked host can strongly bind halide and sulfate oxoanions in competitive aqueous-organic solvent mixtures. Compared to a hydrogen bonding rotaxane analogue, the XB rotaxane exhibits a preference towards lighter halides Cl- ≈ Br- > SO42- > I-.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Zibin Zhang, Yu Yao, Lang He, Tao Hong, Shijun Li, Feihe Huang, Peter J. Stang
Summary: Coordination-driven self-assembly was utilized to construct two metallacycles using a dicarboxylate-functionalized dibenzo-18-crown-6 in combination with either a 0 degrees anthracene-based clip-type acceptor or a 60 degrees phenanthrene-based acceptor. The angularities of these components enabled the formation of a [2 + 2] rectangle and a [3 + 3] triangle, respectively. The synthesis, characterization, and host-guest chemistry of the two metallacycles were described and supported by 31P{1H}, 1H NMR spectra, and electrospray mass spectrometry. (c) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Yu Yao, Jiyong Liu, Peiling Zhang, Kechang Sun, Leqiong Jin, Shijun Li, Feihe Huang, Zhigang Ni, Zibin Zhang
Summary: Self-assembly is a fundamental tool for constructing materials. Copillar[5]arenes, driven by CH center dot center dot center dot 7r interactions, are optimal models for building heteroditopic monomers. The self-assembly manner of copillar[5]arenes in the solid state depends on the competition between the pillar[5]arene cavity and the threading guest moiety or solvent molecules.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Ming Li, Yang Liu, Li Shao, Bin Hua, Mengbin Wang, Haozhong Liang, Niveen M. Khashab, Jonathan L. Sessler, Feihe Huang
Summary: Variable stoichiometry co-crystals are important in solid-state supramolecular chemistry as they allow for the study of structure-property relationships and the synthesis of new scaffolds. In this work, the concept of variable stoichiometry co-crystals is extended to pillararene chemistry, resulting in the construction of a diverse set of supramolecular structures. These co-crystals display different physicochemical properties and can be used for vapochromic-based detection.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Haozhong Liang, Yuting Yang, Li Shao, Weijie Zhu, Xiaofeng Liu, Bin Hua, Feihe Huang
Summary: It is found that using pillar[5]arene (BrP5) as the macrocyclic host to encapsulate nonlinear optical (NLO) materials (OM, DAST, and MNS) can change their solid-state packing and manipulate their centrosymmetric arrangements, achieving second harmonic generation (SHG) in the solid and crystalline states. This research opens a new way to construct solid-state organic NLO materials with potential applications in high-power lasers, optical switches, and imaging.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiaodan Xu, Rui Wang, Dongdong Li, Jiajia Xiang, Wei Zhang, Xueying Shi, Hongxia Xu, Shasha Yao, Jiwei Liu, Shiqun Shao, Zhuxian Zhou, Feihe Huang, Youqing Shen, Jianbin Tang
Summary: In this study, a pH-responsive polymer nanocarrier modified with aminoguanidine was developed for efficient delivery of bortezomib. The nanoparticles exhibited pH-responsive release in the acidic tumor microenvironment and induced immune activation and antigen uptake by dendritic cells. Consequently, they stimulated cytotoxic T lymphocyte infiltration and triggered robust antitumor immune responses, showing potent antitumor efficacy when combined with an immune checkpoint-blocking antibody.
JOURNAL OF CONTROLLED RELEASE
(2023)
Article
Chemistry, Multidisciplinary
Huaqiang Ju, Haoke Zhang, Li Xin Hou, Min Zuo, Miao Du, Feihe Huang, Qiang Zheng, Zi Liang Wu
Summary: We propose a facile strategy to achieve room-temperature phosphorescence in conventional hydrogels by polymerization-induced crystallization of dopant molecules, leading to clusterization-induced phosphorescence. Crown ethers dissolved in a concentrated acrylamide aqueous solution crystallize during polymerization to form large spherulites in the hydrogel, resulting in carbonyl clusters and phosphorescence emission. This strategy is universally applicable to hydrogels with different polymeric matrices and dopant molecules. The development of hydrogels with mechanical and phosphorescent properties holds great potential in the biomedical and engineering fields.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Huangtianzhi Zhu, Junkai Liu, Yitao Wu, Lei Wang, Haoke Zhang, Qi Li, Hu Wang, Hao Xing, Jonathan L. Sessler, Feihe Huang
Summary: In this study, a room-temperature phosphorescence (RTP) system responsive to alkyl halides was described. The system consisted of a meta-formylphenyl-bearing pillar[5]arene derivative that supported effective through-space charge transfer. Treatment with bromoethane enhanced the emission. An isomeric para-formylphenyl-bearing pillar[5]arene system proved ineffective in producing an RTP effect.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Biochemistry & Molecular Biology
Wenting Hu, Binglin Ye, Guocan Yu, Feihe Huang, Zhengwei Mao, Yuan Ding, Weilin Wang
Summary: With the increasing demand for personalized medical care, supramolecular theranostic systems based on cyclodextrins (CDs) have become popular due to their reversible switchable structures, sensitive response to biological stimuli, and ability to integrate multiple capabilities in a programmable manner. This review focuses on the design of various functional modules and interactions in CD-based supramolecular systems for cancer diagnostics and therapeutics. By providing state-of-the-art examples, the review aims to enhance the understanding of the important role of cyclodextrin-based nanoplatforms in advancing supramolecular cancer theranostics.
Review
Polymer Science
Ruoqian Zhang, Rongrong Li, Feihe Huang, Mingming Zhang
Summary: This review summarizes the progress of metallacycle/metallacage-cored supramolecular networks, focusing on the structures connected by covalent or non-covalent interactions. The detailed descriptions of the structures, properties, functions, and applications of such networks are provided to showcase the exciting achievements in this emerging field. The review also highlights the remaining challenges and perspectives to attract more scientists to contribute to this promising area.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Zuping Xiong, Jianyu Zhang, Lei Wang, Yuan Xie, Yipu Wang, Zujin Zhao, Haoke Zhang, Jing Zhi Sun, Feihe Huang, Ben Zhong Tang
Summary: Nonconjugated clusteroluminogens (CLgens), such as proteins and polystyrene, have become increasingly important in photophysics due to their advantages over traditional conjugated dyes in biological applications. However, their weak visible emissions in the aggregate state have hindered their development. This study proposes a strategy to construct a higher-level intramolecular through-space interaction (TSI) in multi-aryl-substituted alkanes, resulting in efficient clusteroluminescence (CL) with high luminescence quantum yield and long emission wavelength.
Article
Multidisciplinary Sciences
Qiong Chen, Zhaoyong Li, Ye Lei, Yixin Chen, Hua Tang, Guangcheng Wu, Bin Sun, Yuxi Wei, Tianyu Jiao, Songna Zhang, Feihe Huang, Linjun Wang, Hao Li
Summary: Controlling the self-assembly on noncovalent components is possible by suppressing entropy loss with templates but this is challenging for covalent components. Here the authors employed directing groups to endow purely covalent molecular building blocks with different conformations which favor the formation of specific self-assembled products.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Bohan Zhao, Jianwei Wang, Li Shao, Yitao Wu, Ming Li, Bin Hua, Feihe Huang
Summary: An efficient adsorptive separation method using nonporous adaptive crystals of perbromoethylated pillar[5]arene (BrP5) for monobromotoluene isomers is reported. The purity of separated m-bromotoluene from an equal volume mixture of m-bromotoluene and o-bromotoluene reaches 96.6% in one cycle, and the adsorbent BrP5 can be reused without losing separation performance.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Saisai Yu, Miao Yang, Yuanhan Liu, Ming Liu
Summary: Membrane separation technology is an efficient and energy-saving alternative for industrial processes. The development of high-performance membrane materials is crucial for membrane separation applications. Porous organic molecular materials, known for their solution processability and stability, have emerged as promising candidates. This review summarizes recent advances in the fabrication of membranes using porous organic molecular materials and highlights their applications in gas separation, ion separation, water treatment, and proton exchange in fuel cells. It also discusses research challenges and future directions for the design and development of high-performance separation membranes.
MATERIALS CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Dan Wu, Jiaqi Lei, Zhankui Zhang, Feihe Huang, Marija Buljan, Guocan Yu
Summary: The synthesis of vital biomacromolecules through the polymerization of small biomolecules to support and multiply life is an emerging field that showcases the diversity and efficiency of chemistry as well as the flexibility and ingenuity of physiological environment. Efforts have been made to design and develop in situ intra/extracellular polymerization reactions, which have found applications in various important research areas, including cell surface engineering, biocompatible polymerization, cell behavior regulation, living cell imaging, targeted bacteriostasis, and precise tumor therapy.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Haozhong Liang, Yuting Yang, Li Shao, Weijie Zhu, Xiaofeng Liu, Bin Hua, Feihe Huang
Summary: In this study, pillar[5]arene was used as a host molecule to encapsulate NLO molecules (OM, DAST, and MNS) in order to change their solid-state packing and manipulate their centrosymmetric arrangements. Experimental results showed that different packing arrangements resulted in different levels of second harmonic generation (SHG). This research provides a new approach to construct solid-state organic NLO materials with potential applications in high-power lasers, optical switches, and imaging.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
