Article
Chemistry, Multidisciplinary
Alica C. Keuper, Kevin Fengler, Florian Ostler, Tobias Danelzik, Dariusz G. Piekarski, Olga Garcia Mancheno
Summary: A new approach to achieve highly enantioselective halogen-bonding catalysis has been developed by designing fine-tuned halogen-halogen interactions. This strategy utilizes both the electron cloud and sigma-hole site of the substrate's halogen substituent to form a tight chiral complex, enabling controlled induction of high levels of chirality transfer. Remarkable enantioselectivities of up to 95:5 e.r. (90% ee) have been achieved in a model dearomatization reaction using tetrakis-iodotriazole multidentate anion-binding catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Sergi Burguera, Antonio Bauza, Antonio Frontera
Summary: This study provides evidence that Hg(II)& sdot;& sdot;& sdot;d(8)[M] interactions should be more accurately described as spodium bonds.
Article
Crystallography
Dmitriy F. Mertsalov, Rosa M. Gomila, Vladimir P. Zaytsev, Mikhail S. Grigoriev, Eugeniya Nikitina, Fedor Zubkov, Antonio Frontera
Summary: This paper reports the synthesis and X-ray characterization of two derivatives containing the four most abundant halogen atoms, aiming to study Ha···Ha halogen bonding interactions. The heavier halogen atoms exhibit anisotropy of electron density, leading to the formation of multiple Ha···Ha contacts in the solid state. The halogen bonding assemblies in both compounds were analyzed using various methods such as DFT calculations, MEP surfaces, QTAIM, NCIplot, and ELF.
Article
Chemistry, Multidisciplinary
Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen
Summary: Neutral halogen-bonded O-I-N complexes were prepared using carbonyl hypoiodites and aromatic organic bases. Modulating the Lewis basicity led to halogen-bonded complexes where the O-I...N bond transforms more into an asymmetric ion pair. X-ray analyses and NMR studies confirmed the geometries of the complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Wei Wang, Xinxin Li, Pan-Pan Zhou, Yao Wang
Summary: A new catalysis platform, supramolecular carbon-bonding catalysis, utilizes weak interactions between carbon centers of catalysts and electron donors to facilitate chemical reactions. By using cyclopropane derivatives with specific functional groups as catalysts, the approach demonstrates general catalysis capability in various benchmark reactions, including a challenging terpene cyclization. Co-crystal structures, comparison experiments, and titrations support a catalysis mode involving carbon-bonding activation of Lewis basic reactants.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Daniel A. Decato, Asia Marie S. Riel, James H. May, Vyacheslav S. Bryantsev, Orion B. Berryman
Summary: This paper experimentally quantifies a Hydrogen Bond-Enhanced Halogen Bond (HBeXB) for the first time, showing that electron-rich halogen bond donors are strengthened most by an adjacent hydrogen bond, and stronger hydrogen bond donors enhance the halogen bond the most. X-ray crystal structures and F-19 NMR titrations support the findings, laying the foundation for future studies on hydrogen bonds and halogen bonds in close proximity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sergey Baykov, Daniil M. Ivanov, Svetlana O. Kasatkina, Bartomeu Galmes, Antonio Frontera, Giuseppe Resnati, Vadim Y. Kukushkin
Summary: The co-crystallization of tetracyanobenzene with haloarenes was studied, and it was found that the stacking interactions and lone pair-pi-hole bonds between the molecules promote the strength of halogen bonding. The stacking interactions increase the ability of haloarenes to act as halogen bonding donors.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Dhananjoy Pal, Tim Steinke, Lukas Vogel, Elric Engelage, Sascha Heinrich, Dana Kutzinski, Stefan M. Huber
Summary: This article describes the synthesis of a mixed chalcogen- and halogen-bond donor and provides a first indication of its catalytic activity in a benchmark reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Vasily Sivchik, Aleksandr Kochetov, Toni Eskelinen, Kristina S. Kisel, Anastasia Solomatina, Elena Grachova, Sergey P. Tunik, Pipsa Hirva, Igor O. Koshevoy
Summary: The luminescent cyclometalated complexes decorated with cyanide ligand can serve as nucleophilic building blocks for halogen-bonded adducts, with noncovalent interactions playing a key role in their photoluminescent properties and excited states. The degree of aggregation via metal-metal interactions determines the optoelectronic properties and photoemissive characteristics of the crystalline materials.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Amila M. Abeysekera, Boris B. Averkiev, Abhijeet S. Sinha, Pierre Le Magueres, Christer B. Aakeroy
Summary: The study found that intramolecular hydrogen bonds in some co-crystals remained intact, while most intermolecular hydrogen bonds in the targets were disrupted. The acceptor sites selected by the halogen bond donors were mainly distributed in N(pyr), O=C, or pi sites.
Review
Chemistry, Multidisciplinary
Binoy K. Saha, Ragima V. P. Veluthaparambath, Vibha G. Krishna
Summary: Halogen interaction is a controversial and important topic in crystal engineering and supramolecular chemistry, involving F, Cl, Br, and I. Lighter and heavier halogens behave differently, and the nature of the interaction depends on the atom covalently bonded to the halogens. This review discusses different types of homo-halogen, hetero-halogen, and halogen-halide interactions, their natures, preferred geometries, as well as various motifs and interchangeability with other functional groups. The review also mentions important applications of halogen interactions.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Ming-Mei Zhou, Jiao He, Hui-Min Pan, Qing Zeng, Hang Lin, Ke-Qing Zhao, Ping Hu, Bi-Qin Wang, Bertrand Donnio
Summary: This study describes a efficient transition-metal-free arene-fluorine nucleophilic substitution reaction for the straightforward synthesis of several Fluorinated Polycyclic Aromatic Hydrocarbons, and reports the investigation of their liquid crystalline and optical properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yuki Yamagishi, Yuichiro Kobayashi, Akiyoshi Horiguchi, Daiki Kitano, Hiroyasu Yamaguchi
Summary: In this study, a supramolecular polysulfide polymer was successfully prepared using metal-ligand interactions. The molecular weight of the resulting polymer was higher than that obtained via conventional polymerization. The disassembly and re-assembly of the polymer were controlled by manipulating the metal-ligand interactions.
Review
Biochemistry & Molecular Biology
Antonio Frontera, Antonio Bauza
Summary: This review gathers several examples of the application of pnictogen and chalcogen bonding interactions in organocatalytic processes, suggesting that it should be considered as a novel, promising tool in the field of organocatalysis.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Laura E. Bickerton, Andrew Docker, Alistair J. Sterling, Heike Kuhn, Fernanda Duarte, Paul D. Beer, Matthew J. Langton
Summary: Synthetic anion transporters have shown great potential as potential anticancer agents and therapeutics for diseases associated with mis-regulation of protein anion channels. Highly active bidentate halogen bonding and chalcogen bonding anion carriers have been reported, demonstrating record nanomolar chloride transport activity and remarkably high chloride over proton/hydroxide selectivity. Computational studies suggest sigma-hole mediated anion recognition and desolvation as crucial for achieving high transport activity and selectivity in synthetic anionophores.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
