New charge-transfer complexes of 1,2,5-chalcogenadiazoles with tetrathiafulvalenes

Chulanova, Elena A.; Radiush, Ekaterina A.; Balmohammadi, Yaser; Beckmann, Jens; Grabowsky, Simon; Zibarev, Andrey V.

doi:10.1039/d2ce01385a

Cited by 5 publications

(5 citation statements)

References 114 publications

(190 reference statements)

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“…Most likely, the parallel disposition is caused by a packing effect of the flat heterocyclic moieties. Similar parallel packing is observed for many telluradiazole derivatives. − ,,− In the β-polymorph, nearly parallel telluradiazole cycles from the neighboring chains are placed even further apart, with the distances of ∼4.2 Å between their planes, to form stacked columns along the [100] direction. The Te···N ChB lengths of ∼2.7 and ∼2.9 Å in both structures are typical. − ,, In multiple experiments, the elongated crystals of the β-polymorph were observed only once.…”

Section: Resultsmentioning

confidence: 57%

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

Pushkarevsky,

Smolentsev,

Wang

et al. 2024

Crystal Growth & Design

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One-dimensional coordination polymers [1•2] ∞ (two polymorphs) and [1 2 •2] ∞ were obtained by cocrystallization of 3,4-dicyano-1,2,5-telluradiazole (1) and N,N,N′,N′-tetramethylethane-1,2-diamine (2). In the presence of Solv (C 6 H 6 , C 5 H 5 N, or C 4 H 4 S), differently colored, depending on the conditions, {[1 2 •2]• Solv} ∞ clathrates were isolated: products synthesized in the light were green, whereas those synthesized in the dark were yellow. In {[1 2 •2]•Solv} ∞ , the Solv molecules occupy cavities formed by methyl groups of 2. With pyridazine, the 1•(1,2-C 4 H 4 N 2 ) 2 discrete complex was synthesized, and no clathrates/complexes were observed with pyrazine (1,4-C 4 H 4 N 2 ) and pyrrole (C 4 H 5 N). In the compounds, 2 connects two 1 or 1 2 by Te•••N chalcogen bonding (ChB), which is decisive for their formation according to quantum theory of atoms in molecules (QTAIM), NBO, and Hirshfeld surface analyses. The ChB features orbital contribution/ polarization. The second-order perturbation energies are structure-dependent, and those for {[1 2 •2]•Solv} ∞ are slightly higher than those for [1•2] ∞ and [1 2 •2] ∞ . Time-dependent density functional theory (TD-DFT) calculations on the X-ray diffraction (XRD) unit cells of green {[1 2 •2]•Solv} ∞ do not reproduce their longest-wavelength absorption, which might indicate minor light-induced side products.

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Section: Resultsmentioning

confidence: 57%

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

Pushkarevsky,

Smolentsev,

Wang

et al. 2024

Crystal Growth & Design

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“…Theoretical UV‐Vis spectra of the isolated [ 1 4 −Hal] − and expected [ 1 −Hal] − were calculated by TD‐DFT [108,109] for their optimized geometries (SI); the double‐hybrid B2PLYP functional [110] was chosen as performing well for related compounds [74,111] . For [ 1 −Hal] − , the calculations embraced both gas phase and MeCN solution with the conductor‐like polarizable continuum model (C‐PCM) [112] for the solvent, and for [ 1 4 −Hal] − , a gas phase (SI).…”

Section: Resultsmentioning

confidence: 99%

“…Theoretical UV-Vis spectra of the isolated [1 4 À Hal] À and expected [1À Hal] À were calculated by TD-DFT [108,109] for their optimized geometries (SI); the double-hybrid B2PLYP functional [110] was chosen as performing well for related compounds. [74,111] For [1À Hal] À , the calculations embraced both gas phase and MeCN solution with the conductor-like polarizable continuum model (C-PCM) [112] for the solvent, and for [1 4 À Hal] À , a gas phase (SI). For [1 4 À Hal] À , comparison of the solid-state (Figure 2) and theoretical (SI) UV-Vis spectra reveal that the calculations strongly underestimate energies of longwavelength electronic transitions in a Hal-dependent way, which should be taken into account in discussing solution spectra of the reaction mixtures.…”

Section: Solution Situation and Synthesesmentioning

confidence: 99%

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

Radiush,

Wang,

Chulanova

et al. 2023

ChemPlusChem

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The [M4–Hal]– (M = the title compound; Hal = Cl, Br, and I) complexes were isolated in the form of salts of [Et4N]+ cation and characterized by XRD, NMR, UV‐Vis, DFT, QTAIM, EDD, and EDA. Their stoichiometry is caused by a cooperative interplay of σ‐hole‐driven chalcogen (ChB) and hydrogen (HB) bondings. In the crystal, [M4–Hal]– are connected by the π‐hole‐driven ChB; overall, each [Hal]– is six‐coordinated. In the ChB, the electrostatic interaction dominates over orbital and dispersion interactions. In UV‐Vis spectra of the M + [Hal]– solutions, ChB‐typical and [Hal]–‐dependent charge‐transfer bands are present; they reflect orbital interactions and allow identification of the individual [Hal]–. However, the structural situation in the solutions is not entirely clear. Particularly, the UV‐Vis spectra of the solutions are different from the solid‐state spectra of the [Et4N]+[M4–Hal]–; very tentatively, species in the solutions are assigned [M–Hal]–. It is supposed that the formation of the [M4–Hal]– proceeds during the crystallization of the [Et4N]+[M4–Hal]–. Overall, M can be considered as a chromogenic receptor and prototype sensor of [Hal]–. The findings are also useful for crystal engineering and supramolecular chemistry.

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“…[53][54][55][56] It is expected that the discovered counterintuitive effect might be of the general character within main group chemistry and find applications in the design and synthesis of new functional materials. Particularly, E/R and E/R' heavier derivatives (E = Se, Te; R = Cl, Br, I) can be used in the design and synthesis of new CT complexes with tetrachalcogenafulvalenes (chalcogen = S, Se, Te) proposed as molecular (photo) conductors; [57,58] and, as in-chain or/and pendant/side groups, in the design and synthesis of redox active ambipolar polymers for organic memristors. [4,5] Overall, this work suggests that the scope of size-dependent effects in chemistry is broader than it is usually discussed, [59] and covers not only nanoparticles but also normal molecules with their isostructural/isoelectronic transformations.…”

Section: Discussionmentioning

confidence: 99%

Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐System

et al. 2023

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2,1,3‐Benzochalcogenadiazoles C6R4N2E (E/R; E=S, Se, Te; R=H, F, Cl, Br, I) and C6H2R2N2E (E/R’; E=S, Se, Te; R=Br, I) are 10π‐electron hetarenes. By CV/EPR measurements, DFT calculations, and QTAIM and ELI‐D analyses, it is shown that their molecular electron affinities (EAs) increase with decreasing Allen electronegativities and electron affinities of the E and non‐hydrogen R (except Cl) atoms. DFT calculations for E/R+e⋅−→[E/R]⋅− electron capture reveal negative ΔG values numerically increasing with increasing atomic numbers of the E and R atoms; positive ΔS has a minor influence. It is suggested that the EA increase is caused by more effective charge/spin delocalization in the radical anions of heavier derivatives due to contributions from diffuse (a real‐space expanded) p‐AOs of the heavier E and R atoms; and that this counterintuitive effect might be of the general character.

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New charge-transfer complexes of 1,2,5-chalcogenadiazoles with tetrathiafulvalenes

Abstract: Five new charge-transfer (CT) complexes of structurally varied 1,2,5-chalcogenadiazoles (monocyclic, 6-5 bicyclic and 6-6-5 tricyclic; chalcogen = S, Se and Te) with tetrathiafulvalenes (TTF and its bis(ethylenedithio) derivative BEDT-TTF) were...

Cited by 5 publications

References 114 publications

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

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

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

Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐System

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