Linear Pentaiodide in the Radical Cation Salt of a Tetrathiafulvalene Bisannulated Macrocycle

Abstract

The cation radical salt of dimethylthiotetrathiafulvalene bisannulated tetraoxatetrathiatetracosane with linear pentaiodide and triiodide counterions was prepared by electrocrystallization. Within the crystal, linear I5 - and I3 - form a cage-like network, in which isolated cation radicals are located. The formation of linear I5 - was also confirmed by the optical spectra.

Synthesis, Structure, and Bonding in Polyiodide and Metal Iodide−Iodine Systems

“…The crystal structures of three compounds containing linear pentaiodide ions have been characterized: [trimesic acid·H 2 O] 10 (H + )(I 5 - ), [1,1'-(propane-1,3-diyl)ferrocenium] 3 (I 3 ) 2 (I 5 ) ( 3.9 ), and (DMT-TTF)(I 3 )(I 5 ). − They can all be described in terms of two iodine molecules coordinated to a central iodide ion. In the two latter structures, the linear pentaiodide ions are incorporated into infinite chains with I 3 - [I 3 - ···I 5 - ···I 3 - , d (I···I) > 3.60 Å].…”

“…. [102][103][104] They can all be described in terms of two iodine molecules coordinated to a central iodide ion. In the two latter structures, the linear pentaiodide ions are incorporated into infinite chains with I 3 -[I 3 -‚‚‚I 5 -‚‚‚I 3 -, d(I‚‚‚I) > 3.60 Å].…”

Molecular self-assembly of 1D infinite polyiodide helices in a phenanthrolinium salt

“…25 Infinite linear chains are less common. They have been registered as weakly interacting I 3 − ⋯I 3 − (intermolecular distance >4.0 Å), 26 linear chains interconnected with I 3 − perpendicular to the propagation axis, 27,28 or a pure linear chain with alternating I-I distances in (Me 4 Sb) 3 I 8 . 29 In the latter example, however, doubts about its structure have been raised on the basis of theoretical calculations.…”

The Formation of High‐Order Polybromides in a Room‐Temperature Ionic Liquid: From Monoanions ([Br5]− to [Br11]−) to the Isolation of [PC16H36]2[Br24] as Determined by van der Waals Bonding Radii

“…[3] However, our understanding of the factors that control polybromide formation is still significantly less well developed than it is for polyiodides. Indeed, of all the halides, only the iodides are comprehensively characterised by vibrational spectroscopic [4] and single crystal X-ray diffractive analyses, [5] with a substantial array of works describing mono- [5b] and polyanions [6] in their varied structural environments both in the solid and liquid states (comprehensively reviewed by Svensson and Kloo [7] ). The lighter polyhalides often present experimentally limiting difficulties due to their highly volatile, corrosive and hazardous nature.…”