Halide Complexes of 5,6‐Dicyano‐2,1,3‐Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding

ChemPlusChem, Год журнала: 2023, Номер 88(11)

Опубликована: Сен. 26, 2023

The [M4 -Hal]- (M=the title compound; Hal=Cl, Br, and I) complexes were isolated in the form of salts [Et4 N]+ cation characterized by XRD, NMR, UV-Vis, DFT, QTAIM, EDD, EDA. Their stoichiometry is caused a cooperative interplay σ-hole-driven chalcogen (ChB) hydrogen (HB) bondings. In crystal, are connected π-hole-driven ChB; overall, each [Hal]- six-coordinated. ChB, electrostatic interaction dominates over orbital dispersion interactions. UV-Vis spectra M+[Hal]- solutions, ChB-typical -dependent charge-transfer bands present; they reflect interactions allow identification individual . However, structural situation solutions not entirely clear. Particularly, different from solid-state ; very tentatively, species assigned [M-Hal]- It supposed that formation proceeds during crystallization Overall, M can be considered as chromogenic receptor prototype sensor findings also useful for crystal engineering supramolecular chemistry.

Язык: Английский

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Polycyclic 1,2,5-chalcogenadiazole dyes: structural, optical, and redox properties in neutral and radical-ion states (chalcogen = S, Se)

Dyes and Pigments, Год журнала: 2025, Номер unknown, С. 112922 - 112922

Опубликована: Июнь 1, 2025

Язык: Английский

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Coordination Polymers between 3,4-Dicyano-1,2,5-telluradiazole and N,N,N′,N′-Tetramethylethane-1,2-diamine: The Decisive Role of Chalcogen Bonding

Crystal Growth & Design, Год журнала: 2024, Номер 24(12), С. 5236 - 5250

Опубликована: Июнь 3, 2024

One-dimensional coordination polymers [1·2]∞ (two polymorphs) and [12·2]∞ were obtained by cocrystallization of 3,4-dicyano-1,2,5-telluradiazole (1) N,N,N′,N′-tetramethylethane-1,2-diamine (2). In the presence Solv (C6H6, C5H5N, or C4H4S), differently colored, depending on conditions, {[12·2]·Solv}∞ clathrates isolated: products synthesized in light green, whereas those dark yellow. {[12·2]·Solv}∞, molecules occupy cavities formed methyl groups 2. With pyridazine, 1·(1,2-C4H4N2)2 discrete complex was synthesized, no clathrates/complexes observed with pyrazine (1,4-C4H4N2) pyrrole (C4H5N). compounds, 2 connects two 1 12 Te···N chalcogen bonding (ChB), which is decisive for their formation according to quantum theory atoms (QTAIM), NBO, Hirshfeld surface analyses. The ChB features orbital contribution/polarization. second-order perturbation energies are structure-dependent, slightly higher than [12·2]∞. Time-dependent density functional (TD-DFT) calculations X-ray diffraction (XRD) unit cells green do not reproduce longest-wavelength absorption, might indicate minor light-induced side products.

Язык: Английский

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Recognition and sensing of Lewis bases by 1,2,5-chalcogenadiazoles

Mendeleev Communications, Год журнала: 2024, Номер 34(3), С. 297 - 306

Опубликована: Май 1, 2024

Язык: Английский

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Electrostatic Surface Potentials and Chalcogen‐Bonding Motifs of Substituted 2,1,3‐Benzoselenadiazoles Probed via 77Se Solid‐State NMR Spectroscopy

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Авг. 23, 2024

Abstract Chalcogen bonds (ChB) are moderately strong, directional, and specific non‐covalent interactions that have garnered substantial interest over the last decades. Specifically, presence of two σ‐holes offers great potential for crystal engineering, catalysis, biochemistry, molecular sensing. However, ChB applications currently hampered by a lack methods to characterize control chalcogen bonds. Here, we report on influence various substituents (halogens, cyano, methyl groups) observed self‐complementary networks 2,1,3‐benzoselenadiazoles. From electrostatic calculations, show surface potentials (ESP) selenium largely influenced electron‐withdrawing character these substituents. Structural analyses via X‐ray diffraction reveal variety geometries binding modes rationalized computed ESP maps, although structure 5,6‐dimethyl‐2,1,3‐benzoselenadiazole also demonstrates steric interactions. 77 Se solid‐state magic‐angle spinning NMR spectroscopy, in particular analysis chemical shift tensors, is found be an effective probe able both structural features systems. We find positive correlation between value maxima at experimentally measured isotropic shift, while skew tensor established as metric which reflective motif.

Язык: Английский

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Chalcogen-Peierls Transition: Single-Crystal-to-Single-Crystal Transition from a Two-Dimensional to a One-Dimensional Network of Chalcogen Bonds at Low Temperature

Bulletin of the Chemical Society of Japan, Год журнала: 2023, Номер 96(7), С. 631 - 635

Опубликована: Май 26, 2023

Abstract Due to inherent structural instability, low-dimensional materials often undergo the Peierls transition upon cooling, which is suppressed by an increase in dimensionality of their solid-state electronic structures using secondary bonding interactions such as chalcogen bonds (ChB). We revealed here that ChB themselves have instability when a atom participates simultaneous formation two ChB, demonstrating for first time Peierls-like (chalcogen-Peierls transition) ChB-based organic solids cooling. Thus, lattice dimerization occurs at 220–230 K changes two-dimensional network into accumulated one-dimensional ribbon tetracyanoquinodimethane fused with [1,2,5]thiadiazoles (1). Negative cooperativity weakened on Se due greater polarizability. selenadiazole analogues (2 and 3) similar chalcogen-Peierls lower temperatures, 160–170 110–120 K, respectively, depending number incorporated (one or two, respectively).

Язык: Английский

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Crystal Engineering, Electron Conduction, Molecular Recognition and Reactivity by Chalcogen Bonds in Tetracyanoquinodimethanes Fused with [1,2,5]Chalcogenadiazoles

Synlett, Год журнала: 2023, Номер 34(17), С. 1978 - 1990

Опубликована: Апрель 12, 2023

Abstract Studies on a series of tetracyanoquinodimethanes (TCNQs) fused with [1,2,5]chalcogenadiazole rings reveals that chalcogen bonds (ChBs), through E•••N≡C (E = S or Se) contacts, are decisive factor in determining their crystal structures, the formation one- two-dimensional networks lateral direction. For anion-radical salts generated by one-electron reduction, electron conduction occurs direction network due to intermolecular electronic interactions involving ChBs. Based reliable synthon for engineering, molecular recognition so solid-state complexes selectively formed certain donors, such as xylenes, among isomers charge-transfer-type clathrate formation. The inclusion cavity might provide reaction environment photoinduced transfer solid state. accommodation multiple conformers overcrowded ethylene exhibiting thermo/mechanochromism is another example novel function can be realized ChBs contacts. Therefore, these chalcogenadiazolo-TCNQs endowed ability form promising materials development functions. 1 Introduction 2 Bis[1,2,5]thiadiazolo-TCNQ (BTDA) 2.1 Chalcogen Bonds Crystal Structures BTDA and its Se Analogues 2.2 Electronic Effects Organic Conductors Consisting 2.3 Molecular Recognition Complexes 2.4 Single-Crystalline-State Photoreactions 2.5 Overcrowded Ethylene Composed Substructure 3 TCNQ Fused [1,2,5]Chalcogenadiazole 3.1 Chalcogenadiazolo-TCNQs 3.2 Chalcogenadiazolo-TCNNQs: An Bond versus Weak C–H•••N≡C Hydrogen 3.3 TCNNQ Derivatives 4 Outlook

Язык: Английский

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1,2,3,4‐Tetrafluorobiphenylene: A Prototype Janus‐Headed Scaffold for Ambipolar Materials

ChemPlusChem, Год журнала: 2023, Номер 89(5)

Опубликована: Дек. 6, 2023

The title compound was synthesized by Ullmann cross-coupling in low yield as the first representative of [n]phenylene containing hydrocarbon and fluorocarbon rings. Stille/Suzuki-Miyaura reactions, well substitution fluorine suitable starting compounds, failed to give same product. geometric electronic structures were studied X-ray diffraction, cyclic voltammetry density functional theory calculations, together with Hirshfeld surface reduced gradient analyses. crystal structure features head-to-tail π-stacking other fluorine-related secondary bonding interactions. From nucleus-independent chemical shifts descriptor, four-membered ring is antiaromatic, six-membered rings are aromatic. Janus molecule highly polarized; fluoro- Lewis π-acidic π-basic, respectively. electrochemically-generated radical cation long-lived characterized electron paramagnetic resonance, whereas anion unstable solution. reveals electrical properties an insulator. On expanding its molecular scaffold towards partially fluorinated [n]phenylenes (n≥2), presumably can be transformed into those semiconductors. In this context, suggested a prototype for ambipolar materials organic electronics spintronics.

Язык: Английский

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Bromination of naphtho[2,3-c][1,2,5]thiadiazole-4,9-dione

Russian Chemical Bulletin, Год журнала: 2024, Номер 73(10), С. 3038 - 3044

Опубликована: Окт. 1, 2024

Язык: Английский

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