Ye Olde supramolecular chemistry, its modern rebranding and overarching trends in chemistry

Dalton Transactions, Journal Year: 2023, Volume and Issue: 53(4), P. 1373 - 1392

Published: Dec. 26, 2023

We can describe current contingency of supramolecular chemistry as "post-halogen bonding", with clear reference to the success σ-hole model and halogen bond concepts. This phase is characterized by a strong push towards new nomenclature for non-covalent interactions, group-by-group one focusing on electrophile. As such increasingly meets IUPAC endorsement, its proposers report resistances ideas, especially in inorganic coordination communities. The whole issue has been generating considerable debate last decade. Herein we fully embrace discussion hope involving larger share relevant Alternative descriptions are here reevaluated, novel views reconnected older ones, it ultimately questioned whether introduction subtending ideas would be beneficial. themes appreciation general trends chemistry, counterintuitive positioning respect existing extension naming from main block d-block elements - key currently unresolved issues discussed. Equivalent, alternative arguably more comprehensive tentatively given, overcome controversies together pursuit higher rewards: shared view forces common language express it.

Language: Английский

---

A combined crystallographic and theoretical investigation of noncovalent interactions in 1,3,4-oxadiazole-2-thione-N-Mannich derivatives: in vitro bioactivity and molecular docking

RSC Advances, Journal Year: 2023, Volume and Issue: 13(48), P. 34064 - 34077

Published: Jan. 1, 2023

Two 1,3,4-oxadiazole-2-thione-N-Mannich derivatives, specifically 5-(4-chlorophenyl)-3-[(2-trifluoromethylphenylamino)methyl]-1,3,4-oxadiazole-2(3H)-thione (1) and 5-(4-chlorophenyl)-3-[(2,5-difluorophenylamino)methyl]-1,3,4-oxadiazole-2(3H)-thione (2), were synthesized then characterized by elemental analysis NMR (1H 13C) spectroscopy the single crystal X-ray diffraction method. The formed weak intermolecular interactions in solid-state structures of these derivatives thoroughly investigated utilizing a variety theoretical tools such as Hirshfeld surface quantum theory atoms molecules (QTAIM). Furthermore, CLP-PIXEL density functional calculations used to study energetics molecular dimers. Numerous C-H⋯S/Cl/F/π interactions, directional C-Cl⋯Cl halogen bond, π-stacking, type C-F⋯F-C contact short F⋯O interaction, help stabilize structure 1. Crystal 2 also stabilizes with several contacts, including N-H⋯S, C-H⋯N//Cl/F highly C1-Cl1⋯C(π) bond C(π)⋯C(π) interaction. In vitro antimicrobial potency compounds 1 was assessed against various Gram-positive Gram-negative bacterial strains pathogenic yeast-like Candida albicans. Both showed marked activity all tested bacteria Escherichia coli lacked inhibitory Pseudomonas aeruginosa. addition, displayed good anti-proliferative hepatocellular carcinoma (HepG-2) mammary gland breast cancer (MCF-7) cell lines. Molecular docking studies revealed binding modes title at active sites prospective therapeutic targets.

Language: Английский

---

Influence of Internal Noncovalent Bonds on Rotational Dynamics

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(32), P. 13030 - 13037

Published: Aug. 3, 2023

While a good deal of information has accumulated concerning the manner in which an intramolecular noncovalent bond can affect relative energies various conformers, less is known about how such bonds might dynamics interconversion between them. A series molecules are constructed symmetrically equivalent conformers containing be interconverted by rotation, energy barrier to computed quantum chemical methods. The rotation CF3 group attached phenyl ring speeded up if Se··F chalcogen formed with SeH or SeF placed ortho position, that present and stabilizes rotational transition state. analogous SnF3 can, on other hand, engage Sn··Se tetrel its global minimum. energetic cost breakage this not fully compensated appearance Other systems were designed placing two rings opposite ends octahedrally disposed SeF4 group. high inhibits their bulky Br atoms positions, but lowered replaced groups either (SeH SeF) pnicogen (AsH2) F reduction closely related strength these bonds.

Language: Английский

---

Structure Directing Factors and Photophysical Properties of Five Cu(I)-Iodide Materials with N-Donor Heteroaromatic Ligands

Published: Jan. 1, 2024

Cu(I)-halide based materials with N-heterocyclic donor ligands are an emerging family of solids that excel at being outstanding light emitters tunable photophysical properties. Interestingly, their properties strongly dependent on the molecular arrangement and electronic distribution therefore, many efforts have been devoted to unveiling rationalizing structure-photophysical relationship. Nevertheless, there is still a lack structure predictability, crystal engineering these growing need. Keeping this in mind, within contribution, we introduced two families donors bearing amide, phenyl, chloro, methyl substituents combine structural directing factors: attractive interactions steric bulkiness. To aim, synthesized five Cu(I)-iodide complexes: 1D coordination polymers [CuI(isn)]n (1) {[CuI(nic)]·ACN}n (2), one tetrameric cubane [CuI(3-phpy)]4 (3), rhomboid dimer [CuI(8-ClQuin)]2 (4) monomer [CuI(1-CH3isoQuin)] (5). easy ligand dissociation marked distortions enabled rearrangements between mentioned arrays. Then, compiled structures contained provided shape map conversion pathway most similar arrangements, cubane, staircase polymer. Finally, 1-5 investigated transitions identified supported by DFT TD-DFT calculations.

Language: Английский

---

Types of noncovalent bonds within complexes of thiazole with CF₄ and SiF₄

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(7), P. 6127 - 6137

Published: Jan. 1, 2024

The five-membered heteroaromatic thiazole molecule contains a number of electron-rich regions that could attract an electrophile, namely the N and S lone pairs lie in molecular plane, π-system areas above plane.

Language: Английский

---