One-Dimensional Diiodine–Iodobismuthate(III) Hybrids Cat₃{[Bi₂I₉](I₂)₃}: Syntheses, Stability, and Optical Properties

Abstract

One-dimensional iodine-rich iodobismuthates­(III), Cat3{[Bi2I9]­(I2)3} [Cat = 1,4-MePy (1) and 1-EtBMAP (2)], feature the highest amount of “trapped” diiodine units in polyhalogen–halometalates of p-block elements. Both complexes have narrow optical band gaps (1.55 and 1.63 eV, respectively) and moderate thermal stability.

Bifurcated Halogen Bonding Involving Diaryliodonium Cations as Iodine(III)-Based Double-σ-Hole Donors

“…The QTAIM analysis demonstrates the presence of appropriate bond critical points (BCPs) for various intermolecular noncovalent interactions in 1 – 3 (Table ). The low magnitude of the electron density (0.002–0.019 au), positive values of the Laplacian of electron density (0.006–0.058 au), and very close to 0 positive energy density (0.001–0.002 au) in these BCPs are typical for noncovalent interactions involving halogen − and gold atoms. , For bifurcated XBs, in addition to the two BCPs that correspond to the halogen–halogen contacts, the ring critical points were observed in the characteristic triangular regions formed by the bond paths. We defined the energies for all studied contacts according to the procedures proposed by Espinosa et al, Vener et al, and Tsirelson et al (the latter approach was developed exclusively for noncovalent contacts involving halogen atoms), and the estimated strength for each individual contact does not exceed 4.1 kcal/mol.…”

Bismuth(III) Iodide Complexes with 1-Ethyl-4-Dimethylaminopyridinium: Structure, Thermal Stability, and Optical Properties

“…As noted earlier [1], the factors affecting the composition and structure of metal halides include the nature of the cation, the salt of which is used in the synthesis, as well as the ratio of reagents and the nature of the solvent [38]. The role of the latter factor has been studied scarcely, although individual examples demonstrating its importance have been described [39].…”

Phosphorescent Complexes of {Mo6I8}4+ and {W6I8}4+ with Perfluorinated Aryl Thiolates featuring Unusual Molecular Structures

“…in these bond critical points, together with estimated strength for the appropriate short contacts (2.1-3.4 kcal/mol) are typical for noncovalent interactions involving iodine atoms in similar chemical systems. [22,23,24,25] The balance between the Lagrangian kinetic energy G(r) and potential energy density V(r) at these (3, À 1) bond critical points reveals these interactions as purely non-covalent if the ratio À G(r)/V(r) > 1 is satisfied, and having some covalent component if À G(r)/V(r) < 1 takes place; [26] judging from this criterion, covalent contribution in intramolecular noncovalent interactions C•••I in 1 is clearly absent (Table S3: À G(r)/V(r) = 1.33 for "short" contact (3.428 Å) and 1.20 for "long" contact (3.558 Å)). The Laplacian of electron density is decomposed into the sum of contributions along the three principal axes of maximal variation, giving the three eigenvalues of the Hessian matrix (λ 1 , λ 2 and λ 3 ), and the sign of λ 2 can be utilized to distinguish bonding (attractive, λ 2 < 0) weak interactions from non-bonding ones (repulsive, λ 2 > 0).…”