Review
Agriculture, Multidisciplinary
Wenjie Li, Weiwei Xu, Siyun Zhang, Jia Li, Juan Zhou, Demei Tian, Jing Cheng, Haibing Li
Summary: Significant progress has been made in the research on drug encapsulation and release based on supramolecular macrocycles, laying a solid foundation for the development of novel nanopesticide preparations.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2022)
Article
Chemistry, Applied
Meng-Qi Wang, Qian Wang, Meng Chen, Da-Hui Qu
Summary: The study successfully fabricated a supramolecular luminescence system with tunable fluorescence emissions ranging from yellow to green by assembling a simple fluorescent molecule, 4-(pyren-1-yl)-1-(4-vinylbenzyl)pyridin-1-ium chloride (PPD), and cucurbit[n]uril (CB[n], n = 7, 8) via host-guest interactions. This system exhibited enhanced emission efficiency and longer fluorescence lifetime, making it suitable for applications in fluorescent ink and potential for information encryption materials.
Review
Chemistry, Multidisciplinary
Takehiro Hirao, Takeharu Haino
Summary: This review introduces the research directions for the synthesis of supramolecular fullerene polymers, including the linear, networked, helical arrays directed by the use of calix[5]arene-fullerene interactions, and the investigation of the calix[5]arene-fullerene interaction for control over the chain structures of covalent polymers.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Shihui Li, Rong Ma, Xin-Yue Hu, Hua-Bin Li, Wen-Chao Geng, Xianglei Kong, Chao Zhang, Dong-Sheng Guo
Summary: Macrocyclic delivery and therapeutics are important topics in supramolecular biomedicine. This study proposes a drug-in-drug strategy, using a functionalized macrocyclic host to encapsulate an active drug, forming a multifunctional supramolecular active pharmaceutical ingredient. This strategy enables synergistic anti-inflammatory effect in the treatment of rheumatoid arthritis.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Shin-ichiro Kawano, Takahiro Harada, Ako Sasaki, Kentaro Tanaka
Summary: A kinetically-locked trinuclear Co(III) macrocycle with large pi-panels was synthesized using Co(II)-assisted self-assembly and subsequent oxidation of the metal centers. The macrocycle has a discrete nanocavity surrounded by three anthracenyl panels, and it acts as a guest receptor for sodium tetraphenylborate.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Andreas Stoy, Malte Juergensen, Christina Millidoni, Chantsalmaa Berthold, Jacqueline Ramler, Sebastian Martinez, Magnus R. Buchner, Crispin Lichtenberg
Summary: Dynamic covalent chemistry is a powerful tool in synthetic chemistry, allowing for reversible generation of novel structural motifs. This study demonstrates the application of dynamic covalent chemistry to heavy p-block elements, expanding the range of compounds that can be accessed using this approach.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hyejin Kwon, Brian S. Newell, Carson J. Bruns
Summary: Cycloparaphenylene nanocarbons (CPPs) are organic semiconductors with controllable structures and unique optoelectronic properties. In this study, CH-pi interactions were found to enable the inclusion of redox-active metallocene guests in CPPs, enhancing stability through additional supramolecular forces. This finding is significant for the design of bespoke nanoelectronics and artificial molecular machines.
Article
Chemistry, Multidisciplinary
Miguel A. Soto, Veronica Carta, Ingrid Suzana, Brian O. Patrick, Francesco Lelj, Mark J. MacLachlan
Summary: Macrocycle engineering is a key topic in supramolecular chemistry. This study combines different approaches and post-synthetic modifications to transform a single tether into multiple rings. The macrocycles undergo redox reactions, allowing for control of conformational changes and host activity, enabling the capture and release of guests, ring transformations, and control of pseudorotaxane-to-pseudorotaxane conversions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Mengqi Du, Hannes A. Houck, Qiang Yin, Yewei Xu, Ying Huang, Yang Lan, Li Yang, Filip E. Du Prez, Guanjun Chang
Summary: The click chemistry reaction between triazolinedione (TAD) and indole derivatives was used to create force-reversible C-N bonds, which enable materials to display reversible stress-responsiveness in real time. This method provides a general strategy to enhance mechanical strength and ductility in covalently crosslinked polymer materials.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Arico Del Mauro, Zoran Kokan, Vladimir Sindelar
Summary: Bambusuril-based [1]rotaxanes were formed quantitatively using a reversible covalent bond and host-guest anion recognition. These novel [1]rotaxanes exhibited a dynamic nature, facilitating carboxylate component exchange reactions in acetonitrile.
CHEMICAL COMMUNICATIONS
(2022)
Article
Nanoscience & Nanotechnology
Xiong Liu, Zhijun Ren, Fangfei Liu, Li Zhao, Qiangjun Ling, Haibin Gu
Summary: Hydrogel-based flexible strain sensors have great potential in various applications such as body movement tracking and disease diagnosis. By utilizing dual network hydrogels, researchers have developed composite hydrogels with self-healing, biocompatibility, stretchability, and high sensitivity, which can be used for monitoring human motions and respiratory movements.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Review
Chemistry, Multidisciplinary
A. Gaston Orrillo, Ricardo L. E. Furlan
Summary: Sulfur plays an important role in dynamic covalent chemistry, especially as part of dynamic sulfur-based bonds (DSBs). DSBs have ideal properties such as high reactivity and good reversibility, which make them highly suitable for the preparation of dynamic covalent systems. They also offer chemical flexibility, opening up multiple applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Thomas A. Sobiech, Yulong Zhong, Daniel P. Miller, Jillian K. McGrath, Christina T. Scalzo, Morgan C. Redington, Eva Zurek, Bing Gong
Summary: The article presents experimental results on the binding of a rigid aromatic oligoamide macrocycle with DABCO-based cationic guests in highly polar DMF, demonstrating strong positive cooperativity. The unusually strong positive cooperativity mechanism is verified through various experimental methods. This host-guest system provides a tunable platform for studying molecular interactions and constructing stable supramolecular assemblies due to its exceptional positive cooperativity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Nobuharu Iwasawa, Kosuke Ono
Summary: By utilizing the dynamic nature of boronic ester formation, a variety of unique boron-containing 3D structures were successfully constructed, revealing characteristic features of the system. The synthesized boronates were further explored for their functions in host-guest chemistry, kinetic connection, characteristic dynamic behaviors, and supramolecular catalysis.
Review
Chemistry, Multidisciplinary
Ze-Wei An, Rui Xue, Kang Ye, Hui Zhao, Yang Liu, Peng Li, Zhen-Ming Chen, Chong-Xing Huang, Guo-Hua Hu
Summary: In order to meet more application requirements, improving the mechanical properties and self-healing efficiency has become the focus of current research on self-healing PU. To address the competitive relationship between self-healing ability and mechanical properties, growing studies have combined dynamic covalent bonding with other self-healing methods to construct the PU structure.
Article
Chemistry, Multidisciplinary
Philipp Erdmann, Lutz Greb
Summary: The global Lewis acidity and effective Lewis acidity often have poor correlation, mainly due to the influence of deformation energy. Through theoretical and experimental analysis, the relationship between global Lewis acidity and effective Lewis acidity is identified.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Marcel Schorpp, Ravi Yadav, Daniel Roth, Lutz Greb
Summary: This paper describes a strategy to unleash Lewis superacidity by electromerism, where coordinating a Lewis base to Delta-calix[4]pyrrolato-antimony(III) triggers a ligand redox-noninnocent coupled transfer into antimony(V)-state that exhibits Lewis superacidic features. This approach of Lewis acidity by electromerism establishes a concept of potential generality for powerful yet robust reagents and on-site substrate activation approaches.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Thaddaeus Thorwart, Deborah Hartmann, Lutz Greb
Summary: In this study, a novel Lewis acid was reported and successfully applied in dihydrogen activation, which has been elusive for non-planar Lewis acid. This research result is important for understanding the mechanism of FLP reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Nils Ansmann, Thaddaus Thorwart, Lutz Greb
Summary: The Lewis superacid bis(perchlorocatecholato)silane catalyzes C-O bond metathesis of alkyl ethers with high efficiency, enabling chemoselective ring contractions of macrocyclic crown ethers and unprecedented ring-closing metathesis of polyethylene glycols for polymer-selective degradation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Deborah Hartmann, Taddaeus Strunden, Lutz Greb
Summary: Treatment of Si(cat(Cl))(2)(MeCN)(2) with TMP or hppH and CO2 forms silicon carbamates. The hapticity at silicon and reactivity of the carbamates are determined by the Lewis base used. Treatment of the carbamates with a Bronsted acid liberates CO2 and reactivates the superacidic behavior.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Daniel Roth, Thaddaeus Thorwart, Clara Douglas, Lutz Greb
Summary: The first bis(amidophenolato)phosphonium salts were prepared and found to be highly Lewis acidic, with a strong affinity for fluoride and hydride ions. This affinity enabled the salts to undergo new reactions and expand their reactivity portfolio. The properties and reactions were thoroughly investigated through theory and experiments.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Selina Hollstein, Philipp Erdmann, Andreas Ulmer, Henrik Loew, Lutz Greb, Max von Delius
Summary: The dynamic covalent chemistry of the Si-O bond has unique opportunities but is rarely used to assemble discrete molecular architectures, possibly due to the harsh conditions required for exchange reactions at silicon in aprotic solvents. In this study, we provide a comprehensive account on the reaction of trialkoxysilanes with alcohols and identify mild conditions for rapid exchange in aprotic solvents. We uncover, understand, and exploit the effects of substituents, solvent, and salt for the construction of sila-orthoester cryptates, which show a sharp, divergent pH-response attractive for future applications beyond host-guest chemistry, such as drug delivery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Rezisha Maskey, Thaddaeus Thorwart, Simone F. Ebel, Angelina Jocic, Deborah Hartmann, Lutz Greb
Summary: Stable metal-free diradicaloids with modifiable nitrogen-containing frameworks can be synthesized through Lewis acid-base pair formation. This method allows for the one-step synthesis of diradicaloids with rationally adjustable diradical character, presenting great potential for various applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Qingqing Luo, Lutz Greb
Summary: Organosilanes are crucial products in the chemical industries, but their bulk production starting from silica has a significant ecological impact due to energy consumption and hazardous by-products. In this study, a redox-neutral, one-pot silicon-carbon bond formation process was developed using catechol-mediated SiO2 depolymerization and nucleophilic substitution. By optimizing the steps, a 76% yield of SiPh4 was achieved on a large scale. This success encourages further research on energy- and waste-efficient organosilane production.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nils Ansmann, Joshua Muench, Marcel Schorpp, Lutz Greb
Summary: A novel chelating Lewis acidic bis(amidophenolato)silane is introduced as a strong Z-type ligand in this study, enabling the characterization of the first anionic [Pd(0)-X]- ate complex. The compounds exhibit a highly unusual square planar coordination and have important implications in Pd-catalyzed cross-coupling reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ravi Yadav, Paul Janssen, Marcel Schorpp, Lutz Greb
Summary: Anti-van't Hoff-Le Bel configured p-blockelementspecies possess intrinsically high reactivity and are thus challenging to isolate. Consequently, numerous elements in this configuration, including square-planar germanium(IV), remain unexplored. Herein, we follow a concept to reach anti-van't Hoff-Le Bel reactivity by ligand dissociation from a rigid calix[4]pyrrole germanein its bis(thf) adduct. While the macrocyclic ligand assures square-planar coordination in the uncomplexed form, the labile thf donors provide robustness for isolation on a multigram scale. Unique properties of a low-lying acceptor orbital imparted to germanium(IV) can be verified, e.g., by isolating an elusive anionic hydrido germanate and exploiting it for challenging bond activations. Aldehydes, water, alcohol, and a CN triple bond are activated for the first time by germanium-ligand cooperativity. Unexpected behaviors against fluoride ion donors disclose critical interferences of a putative redox-coupled fluoride ion transfer during the experimental determination of Lewis acidity. Overall, we showcase how ligand lability grants access to the uncharted chemistry of anti-van't Hoff-Le Bel germanium(IV) and line up this element as a member in the emerging class of structurally constrained p-block elements.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Daniel Roth, Alexander T. Radosevich, Lutz Greb
Summary: A series of structurally constrained phosphenium ions based on pyridinylmethylamidophenolate scaffolds are capable of undergoing P(III)/P(V) oxidative addition reactions with C-H bonds in alkynes, alkenes, and arenes. The reactions are reversible and involve isomerizations and phosphorus-ligand cooperative effects.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Lutz Greb
Summary: In recent decades, numerous strategies have been developed to enhance the reactivity and properties of p-block elements. This Account focuses on our approaches to controlling p-block elements in their normal oxidation states using distinct ligands. Catecholato ligands on silicon, germanium, or phosphorus offer a range of rewarding properties, such as Lewis superacidity. The synthesized species can be utilized for catalysis and bond activation, enriching the chemistry of main-group elements.
Article
Chemistry, Multidisciplinary
Thaddaeus Thorwart, Lutz Greb
Summary: The silicon-carbon bond is crucial for synthetic transformations, but reversible C-H silylations have been elusive. This study demonstrates the successful CH-bond silylation of heterocycles and terminal alkynes using specific silane reagents. The reaction can be reversed by adding a silicon donor, providing a new approach to C-H silylation. This research has important implications for the development of reversible silicon-carbon bond formations.
Article
Chemistry, Multidisciplinary
Lukas M. Sigmund, Eliane Engels, Nick Richert, Lutz Greb
Summary: In this study, the synthesis, characterization, and reactivity of calix[4]pyrrolato gallates, which consist of square planar-coordinated gallium(iii) atoms, were reported. Unusual structural constraint-induced Lewis acidity and fully reversible metal-ligand cooperative capture of CO2 were revealed by both experimental and computational methods.
