Review
Chemistry, Multidisciplinary
Yohei Haketa, Kazuhisa Yamasumi, Hiromitsu Maeda
Summary: The pairing and ordered arrangement of charged pi-electronic systems are achieved through the synergistic effects of electrostatic and dispersion forces. Various methods, including covalent bonding and noncovalent ion complexation, are used to prepare charged pi-electronic systems. These systems exhibit diverse ion pairs and intriguing characteristics.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Yoshifumi Sasano, Hiroki Tanaka, Yohei Haketa, Yoichi Kobayashi, Yukihide Ishibashi, Tatsuki Morimoto, Ryuma Sato, Yasuteru Shigeta, Nobuhiro Yasuda, Tsuyoshi Asahi, Hiromitsu Maeda
Summary: Charged pi-electronic species were observed to develop stacking structures based on electrostatic and dispersion forces, with the concept of (i)pi-(i)pi Interaction introduced to describe the interactions in these structures. The energy decomposition analysis revealed the importance of electrostatic and dispersion forces in stabilizing the stacking of pi-electronic ions, as observed through crystal-state absorption spectra and transient absorption spectroscopy.
Article
Chemistry, Multidisciplinary
Na Luo, Yu-Fei Ao, De-Xian Wang, Qi-Qiang Wang
Summary: The article briefly reviews the emergence and development of anion-pi interactions, emphasizing the concept of anion-pi catalysis and key progress in this area. The content is organized based on the role of anion-pi interactions in catalysis, from ground-state and transition-state stabilization to cooperative pi-face activation. A concluding remark and outlook on future development are also provided.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Luka Baresic, Davor Margetic, Zoran Glasovac
Summary: The reaction of furfuryl guanidines with dienophiles showed a strong reaction dependence on the nucleophilicity of the counterion and the structure of guanidine, allowing for control over the selectivity of the reaction products.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Organic
Lukas Janecky, Athanasios Markos, Blanka Klepetar, Petr Beier
Summary: 4-Aryl-5-allyl-N-fluoroalkyl-1,2,3-triazoles were synthesized through a three-component reaction of fluoroalkyl azides, copper acetylides, and allyl halides. These compounds underwent aluminum halide-mediated transformation to N-(4-halo-2-aryl-cyclopentenyl) imidoyl halides by cyclization of vinyl cation intermediates, followed by halide capture. The cyclic products could be further utilized for the synthesis of N-alkenyl amides, amidines, isoquinolines, and tetrazoles, or for the subsequent modification of the cyclopentene ring.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Kee Sung Han, Nathan T. Hahn, Kevin R. Zavadil, Nicholas R. Jaegers, Ying Chen, Jian Zhi Hu, Vijayakumar Murugesan, Karl T. Mueller
Summary: This study investigates the impact of different ether solvent structures on the interactions between multivalent cations and anions in electrolytes, revealing that anions coordinate more readily with divalent cations in cyclic ethers.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Inorganic & Nuclear
Alexander Gehlhaar, Eduardo Schiavo, Christoph Woelper, Yannick Schulte, Alexander A. Auer, Stephan Schulz
Summary: Using a combination of NMR, single crystal X-ray diffraction (sc-XRD), and quantum chemistry, this study demonstrates the structure-directing role of London Dispersion (LD) in the dibismuthane compound Bi(2)Naph(2) (1). The absence of pi...pi interactions in the solid-state and the influence of the pnictogen atom on London dispersion strength in the entire series of dipnictanes highlight the importance of LD in heavy main group element chemistry.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiaolin Yin, Chunmei Liu, Shuang Liu, Mengmeng Cao, Jeremy M. Rawson, Yan Xu, Bin Zhang
Summary: This study successfully designed a series of copper(I) halide complexes with high luminescence performance by introducing functionalized π-conjugated bridging moieties. The experimental results show that these complexes exhibit orange-red emission in the solid state, with high photoluminescence quantum yields and short decay times.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Physical
Aiswarya M. Parameswaran, Anto James, Adil Aboobacker, Rotti Srinivasamurthy Swathi
Summary: This study addresses the challenges of extended conjugation and design of all-carbon neutral anion receptors. Using computations on anion-pi complexes of halide ions with graphynes, the researchers reveal the functional relevance of graphynes as anion receptors and assert that anion-pi interactions are not solely dominated by electrostatic interactions. Polarization components play a crucial role in governing the binding of anions to graphynes.
Article
Chemistry, Multidisciplinary
Yuhong Mao, Songhao Guo, Xu Huang, Kejun Bu, Zhongyang Li, Phuong Q. H. Nguyen, Gang Liu, Qingyang Hu, Dongzhou Zhang, Yongping Fu, Wenge Yang, Xujie Lu''
Summary: Organic-inorganic halide perovskites have unique electronic configurations and high structural tunability, making them promising for photovoltaic and optoelectronic applications. This study investigates the role of organic-inorganic interactions in determining the structural and optical properties by employing pressure tuning in a lead halide perovskite.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Loai Al Sheakh, Thomas Niemann, Alexander Villinger, Peter Stange, Dzmitry H. Zaitsau, Anne Strate, Ralf Ludwig
Summary: The structural versatility of halide salts can be controlled by the nature of hydrogen bonding interactions. Two types of hydrogen bonding, 'intra-ionic' and 'inter-ionic', are observed in the X-ray structures of these salts. Additionally, a third type of hydrogen bonding is found in some molten halide salts.
Article
Multidisciplinary Sciences
Matteo Savastano, Maria Dolores Lopez de la Torre, Marco Pagliai, Giovanna Poggi, Francesca Ridi, Carla Bazzicalupi, Manuel Melguizo, Antonio Bianchi
Summary: In this study, we prepared complexes of a high explosive anion (picrate) with potentially explosive s-tetrazine-based ligands to advance the understanding of the lone pair-pi interaction. By presenting XRD structures of 4 novel detonating compounds and studying their thermal and explosive properties, this research demonstrates the effectiveness of using lone pair-pi contacts in crystal engineering, even for high explosives, and highlights the importance of supramolecular architecture in determining their properties. The in silico explosion properties studied in this research also contribute to improving the safety of high-energy materials.
Article
Chemistry, Inorganic & Nuclear
Irina A. Shentseva, Nikita A. Korobeynikov, Andrey N. Usoltsev, Igor D. Gorokh, Alexander S. Novikov, Ilya V. Korolkov, Maxim N. Sokolov, Sergey A. Adonin
Summary: A series of haloantimonate complexes were obtained by the reactions between halometalate-containing solutions (Sb2O3 in HCl or HBr) and halide salts of halogensubstituted quinolinium cations. The structures were determined by X-ray diffractometry, and the non-covalent interactions in the crystalline state were analysed using theoretical methods.
Article
Chemistry, Multidisciplinary
Xiang Li, Yao Long, Chong Zhang, Chengguo Sun, Bingcheng Hu, Pengfei Lu, Jun Chen
Summary: The stabilization mechanism of cyclo-N-5(-)-containing metal hydrates, including [Na(H2O)(N-5)]center dot 2H(2)O (Na-cyclo-N-5(-)) and [Mg(H2O)(6)(N-5)(2)]center dot 4H(2)O (Mg-cyclo-N-5(-)), has been investigated using first-principles calculations. The results show that Mg-cyclo-N-5(-) is more stable than Na-cyclo-N-5(-), and hydrogen bonding plays a crucial role in stabilizing both the crystals and the cyclo-N-5(-) molecules. These findings provide valuable insights for the future design and synthesis of cyclo-N-5(-)-containing high-energy-density materials.
Article
Chemistry, Multidisciplinary
Hao Gong, Cheng Zhang, Takuya Ogaki, Hiroyuki Inuzuka, Daisuke Hashizume, Daigo Miyajima
Summary: AC3Ts, a substructure of Tz-GCN, can capture protons as organic superbases and exhibit unique anion-pi interactions that alter their ionization potentials. These features are expected to expand the usage scope and possibilities for GCNs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Peng Wu, Jas S. Ward, Kari Rissanen, Carsten Bolm
Summary: Copper-catalyzed cross-coupling reactions of alpha-bromoaryl NH-sulfoximines with elemental sulfur were used to synthesize benzo[d][1,3,2]dithiazole-1-oxides, which belong to a new class of three-dimensional heterocycles. The reactions exhibited good functional group and heterocycle tolerance under mild conditions. Moreover, the initial cross-coupling products could be converted to unprecedented cyclic sulfonimidamides derivatives through imination/oxidation. Additionally, a seven-membered heterocycle was obtained by a ruthenium-catalyzed ring-expansion with ethyl propiolate.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Christian Schumacher, Jas S. Ward, Kari Rissanen, Carsten Bolm, Mohamed Ramadan El Sayed Aly
Summary: Cholesterol can react under Appel conditions to form 3,5-cholestadiene and 313-bromocholest-5-ene, which deviates from the stereochemistry of the standard Appel mechanism due to the involvement of A5 pi-electrons. However, the subsequent azidolysis of 313-bromocholest-5-ene proceeds mainly by Walden inversion, resulting in the formation of 3a-azidocholest-5-ene. The structures of the products were confirmed by X-ray crystallography and the NMR data matched the reported data.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Rene Hommelsheim, Sandra Bausch, Arjuna Selvakumar, Mostafa M. Amer, Khai-Nghi Truong, Kari Rissanen, Carsten Bolm
Summary: Copper(I)-catalyzed domino reactions of 2-azido sulfoximines with 1-iodoalkynes afford fused triazolyl-containing benzothiadiazine-1-oxides in one step with high yields. This method exhibits broad functional group tolerance and allows the synthesis of two fused heterocyclic rings. Mechanistic investigations reveal the involvement of a copper pi-complex and an iodinated triazole intermediate in the reaction sequence.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jas S. Ward, Elina I. Sievanen, Kari Rissanen
Summary: Solid-state NMR was used to study a series of Barluenga-type iodine(I) [L-I-L]PF6 complexes (L=pyridine, 4-ethylpyridine, 4-dimethylaminopyridine, isoquinoline) and their respective non-liquid ligands (L), precursor silver(I) complexes, and N-methylated pyridinium and quinolinium hexafluorophoshate salts. The results were compared to solution studies and single-crystal X-ray structures. Practical considerations were discussed to encourage wider utilization of this technique in the future as the first study of its kind on the solid-state NMR behavior of halogen(I) complexes.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Kwaku Twum, Sanaz Nadimi, Frank Boateng Osei, Rakesh Puttreddy, Yvonne Bessem Ojong, John J. Hayward, Kari Rissanen, John F. Trant, Ngong Kodiah Beyeh
Summary: In this study, the formation of a three-component halogen-bonded ternary assembly in a protic polar solvent system is achieved by utilizing the binding of fused aromatic N-heterocycles in an open resorcinarene cavity to template the assembly. This approach overcomes the challenges posed by the overwhelming quantity of competing solvent.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Shilin Yu, Khai-Nghi Truong, Marcel Siepmann, Arto Siiri, Christian Schumacher, Jas S. Ward, Kari Rissanen
Summary: A series of LH[Z-I-Z] halogen(I) complexes were synthesized and characterized. These complexes consist of a [N-I-N]- anion with a three-center-four-electron (3c-4e) halogen bond, and a hydrogen bonding or inert cation. The symmetric [N-I-N]- anion is structurally equivalent to its cationic analogue [N-I-N]+. However, the [N-I-N]- complexes with a hydrogen bond to only one saccharinato moiety showed asymmetry in the N-I bond lengths, similar to the asymmetric heteroleptic [N-I-N]+ complexes.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Guillermo Romo-Islas, Jas S. Ward, Kari Rissanen, Laura Rodriguez
Summary: The use of heterometallic Au/Cu systems with metallophilic contacts is ideal for obtaining red phosphorescent materials. The synthesized compounds have an ionic character due to the reaction of gold-(I) complexes with copper-(I) salts, and the counterion affects the emission wavelength. These compounds have been tested as photosensitizers for generating singlet oxygen.
INORGANIC CHEMISTRY
(2023)
Article
Plant Sciences
Emanuel T. Mahambo, Colores Uwamariya, Masum Miah, Leandro da Costa Clementino, Luis Carlos Salazar Alvarez, Gabriela Paula Di Santo Meztler, Edward Trybala, Joanna Said, Lianne H. E. Wieske, Jas S. Ward, Kari Rissanen, Joan J. E. Munissi, Fabio T. M. Costa, Per Sunnerhagen, Tomas Bergstrom, Stephen S. Nyandoro, Mate Erdelyi
Summary: Six new crotofolane diterpenoids (1-6) and 13 known compounds (7-19) were isolated from Croton kilwae. The structures of the new compounds were determined by analyzing spectroscopic and mass spectrometric data. Some of the compounds exhibited antiviral, antibacterial, and antimalarial activities.
JOURNAL OF NATURAL PRODUCTS
(2023)
Article
Chemistry, Organic
Xianliang Wang, Kari Rissanen, Carsten Bolm
Summary: N-Trifluoroacetylated (N-TFA) sulfoximines react with 1-trifluoromethylstyrenes in a one-pot domino reaction to give fluorinated 5,6-dihydro-1,2-thiazine 1-oxides in good to high yields. The process involves three sequential reaction steps that can be characterized as (1) nucleophilic allylic substitution (S(N)2 '), (2) hydrolysis, and (3) intramolecular nucleophilic vinylic substitution (SNV). The products can further be modified by defluorination. The molecular structure of the resulting product was confirmed by X-ray crystallographic analysis.
Article
Chemistry, Multidisciplinary
Kari Rissanen, Jas S. Ward
Summary: This study synthesized new iodine(I) complexes using silver(I) complexes and explored the influence of different functional substituents. The properties of these rare iodine(I) complexes containing 3-substituted pyridines were compared to their more prevalent 4-substituted counterparts.
Article
Chemistry, Multidisciplinary
Sanna Komulainen, P. U. Ashvin Iresh Fernando, Jiri Mares, Anne Selent, Roya Khalili, Paul T. Cesana, Andreas Ebeling, Anu M. Kantola, Ngong Kodiah Beyeh, Kari Rissanen, Brenton DeBoef, Perttu Lantto, Ville-Veikko Telkki
Summary: Functionalized cages encapsulating xenon atoms enable highly sensitive, background-free molecular imaging through HyperCEST 129Xe MRI. We introduce a class of potential biosensor cage structures based on two resorcinarene macrocycles bridged either by aliphatic carbon chains or piperazines. Computational predictions and experimental results confirm Xe encapsulation in the aliphatically bridged cage and double encapsulation in the piperazine-bridged resorcinarene.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Teresa M. Karl, Samir Bouayad-Gervais, Julian A. Hueffel, Theresa Sperger, Sebastian Wellig, Sherif J. Kaldas, Uladzislava Dabranskaya, Jas S. Ward, Kari Rissanen, Graham J. Tizzard, Franziska Schoenebeck
Summary: Due to the unknown correlation between a metal's ligand and its resulting preferred speciation in terms of oxidation state, geometry, and nuclearity, the rational design of multinuclear catalysts is still challenging. In this study, we employed an assumption-based machine learning approach to accelerate the identification of suitable ligands for trialkylphosphine-derived dihalogen-bridged Ni-(I) dimers. We experimentally verified the predictions, synthesized novel Ni-(I) dimers, and explored their potential in catalysis, achieving C-I selective arylations of polyhalogenated arenes with competing C-Br and C-Cl sites in under 5 min at room temperature using the newly developed dimer, [Ni-(I)(& mu;-Br)PAd(2)(n-Bu)](2), which has not been met with alternative dinuclear or mononuclear Ni or Pd catalysts so far.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yiwei Gong, Jas S. Ward, Kari Rissanen, Florian F. Mulks
Summary: Site-selective functionalization of pyridines is crucial for the synthesis of pharmaceuticals and materials. We introduce diiminium pyridine adducts as convenient and potent Lewis acids, and report the selective addition of tributylphosphine to the 4-position of pyridine. This finding advances the utilization of diiminium units as organic reagents or catalysts for pyridine functionalization. Computational models provide valuable insights for future investigations in this area.
Article
Chemistry, Multidisciplinary
Rene Hommelsheim, Sandra Bausch, Robin van Nahl, Jas S. Ward, Kari Rissanen, Carsten Bolm
Summary: A variety of 3-amino-substituted benzothiadiazine oxides were synthesized via a one-step palladium-catalyzed cascade reaction of 2-azido sulfoximines with isonitriles. The desired heterocycles were obtained in good to excellent yields using very low catalyst loadings and short reaction times. This protocol provides direct access to precursors for pharmaceutically relevant sulfoximines.
Article
Chemistry, Multidisciplinary
Milla Mattila, Kari Rissanen, Jas S. Ward
Summary: Three chiral carbonyl hypoiodites were synthesized from N-protected (S)-valine and formed ligand-stabilised (S)-valinoyl hypoiodite complexes with 4-dimethylaminopyridine, 4-pyrrolidinopyridine, and 4-morpholinopyridine as stabilising ligands. The structures of the complexes were determined through NMR (H-1, C-13, H-1-N-15 HMBC) and single crystal X-ray diffraction analysis.
CHEMICAL COMMUNICATIONS
(2023)
