New cation-anion interaction motifs, electronic band structure, and electrical behavior in .beta.-(ET)2X salts [ET = bis(ethylenedithio)tetrathiafulvalene; X = dichloroiodide, chlorobromoiodide]

The Binary Iodine‐Chlorine Octahalide Series [InCl8−n]2− (n=3, 3.6, 4)

“…These each have a band at 305–317 cm −1 and a band at 288–295 cm −1 . [NBu 4 ]ICl 2 was reported to have a band at 266 cm −1 and a very strong band at 221 cm −1 . These reports, in combination with our calculations, allow us to assign the bands for 2 and also confirm the trihalide‐pentahalide nature of this octahalide.…”

“…[ NBu 4 ]ICl 2 was reported to have ab and at 266 cm À1 and av ery strong band at 221 cm À1 . [24] These reports,i nc ombination with our calculations, allow us to assign the bands for 2 and also confirm the trihalide-pentahalide nature of this octahalide. Thus, the highest energy band (316 cm À1 )c an be ascribed to symmetric stretching of the strong IÀCl bonds in the pentahalide (mode 18 in Figure 8; this is as trongb and in the Raman at 320 cm À1 )a nd the next higheste nergy band (289 cm À1 )t ot he asymmetrics tretch( mode 17) of the pentahalide.…”

Construction of Ternary Iodine–Bromine–Chlorine Octahalides

“…[7,8] Interestingly,t he number of confirmed (by X-ray diffraction) ternary interhalides to date has been limited to one example,t he classical [BrICl] À trihalide. [9,10] Yagi andP opov claimed the synthesis of the pentahalide [I 2 Cl 2 Br] À by the reaction of [ICl 2 ] À with IBr or [BrICl] À with ICl, which seem reasonable syntheses;h owever,t here is no structural reporta nd only one IR band (at 294 cm À1 )w as reported. [11] As imilar claim for the [ClI 4 ] À pentahalide has been shown to be am ixture of [I 5 ] À and [ICl 2 ] À .…”

“…Although the halogen bonds are relativelyw eak, the terminal IÀXd istances are, as expected, shortert han the internal trihalide IÀXd istances: 2.509(7) versus 2.66(5) for IÀCl, and 2.655(7) versus 2.71(2) for IÀBr.T hese can be compared to reported distances for isolated [BrICl] À of 2.571(3)/2.566(3) for IÀCl, and 2.638(3)/2.647(3) for IBr. [9] The structure of 4 is significantly disordered;t he Br 2 is disordered like 1 (with 50:50 occupancy) due to interactions with the CÀN p holes and the [BrICl] À trihalides are disordered like 3 ( Figure 5). It is possible that all 8c ombinations are presenti n the solid state;h owever,w ef avor the structure shown in Figure5 (bottom).…”

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

“…[165] Other examples of this anion have only been obtained in low-dimensional organic conductors of bis(ethylenedithio)tetrathiofulvalene (BEDT-TTF) salts with trihalide counterions and are therefore disordered, or rather ac ombination of different anions. [166][167][168][169][170]183] [174] Polyinterhalogen anions of F À and BrF 3 : As pecial case that extends the definition of an on-classical polyinterhalide can be formulated if the central atom acts as abridging ligand between several tetratomic interhalogen compounds,namely in [Br 2 F 7 ] À or [Br 3 F 10 ] À . [Br 2 F 7 ] À was first described in 1976 by Sukhoverkhov et al, [184] who studied the BrF 3 /CsF/HF ternary system and reported the IR spectrum of the CsBr 2 F 7 phase.T he solid-state structure of CsBr 2 F 7 was reported in 2013 by Kraus et al [128] Thecentral fluorine atom bridges the two bromine atoms of the BrF 3 molecules and almost forms as quare-pyramidal structure.H owever,i nc ontrast to previous Raman spectroscopic investigations of Stein et al, [185] the structure neither shows aplanar anion, nor alinear Br-mF-Br unit.…”