Synthesis of tetrahalide dianions directed by crystal engineering

Abstract

Crystal engineering provides tools to the rational design of materials with desired structures or properties. We have exploited the analogy between hydrogen bonds and halogen bonds to trap I 2 in the channels of crystal structures, thus stabilizing the otherwise unfavourable tetrahalides via charge transfer interactions. CrystEngCommThis journal is

Stabilization of polyiodide chains via anion⋯anion interactions: experiment and theory

“…We have recently been able to stabilize the rare [19][20][21] tetrahalide dianions [X⋯I-I⋯X] 2− (X = Cl, Br, I) in a templating macrocycle. 22 In this contribution, we report the synthesis and structural characterization of the tyrosinium (Tyr) polyiodide hydrate 1 with formal composition (Tyr + ) 4 I 16 4−…”

Crystal structure of 4,4′-(disulfanediyl)dipyridinium chloride triiodide

“…Labelled interactions are described according to Table 1. parent [I 2 Cl] À anion [for example I� � �Cl = 3.158, 3.047 A ˚in the structures with CSD codes BEQXEA (Wang et al 1999) and BOJYIL (Pan et al 2019), respectively] and [Cl 2 I 2 ] 2dianions [3.070 and 3.242 A ˚in DOXDOL (Buist & Kennedy, 2014) and JUPCAA (Pan et al 2015), respectively]. These Cl� � �I interactions, shown in Fig.…”

Iodine Clathrated: A Solid‐State Analogue of the Iodine–Starch Complex

“…The structurally unstable [Cl•••I-I•••Cl] 2dianions have previously found to be stabilized by the hydrogen bonded framework in a sulfadiazine hydrochloride salt. [27] The [Cl•••I-I•••Cl] 2dianions have also been successfully used to construct the first purely halogen bonded dimeric capsule structure. [16] The average Cl•••Cl distance in this case was about 9.8 Å, very similar with that of the reported ones .…”

“…[16] The average Cl•••Cl distance in this case was about 9.8 Å, very similar with that of the reported ones . [16,27] The phenomenon in the DAO•HCl-I2 of iodine molecules entrapped in the helical organic channel evokes the comparison the iconic starch-iodine system. The similar size of the helical channels [28] might guide the similar arrangement of the inclusion iodine.…”