Halogen bonded metal bis(dithiolene) 2D frameworks

Abstract

Short and directional I⋯S halogen bonding interactions in iodinated bis(dithiolene) complexes lead to the crystallization of 2D or 3D anionic frameworks.

The Chloroazaphosphatrane Motif for Halogen Bonding in Solution

“…Among the σ–hole interactions, XB (halogen bonding) interaction appears as the most studied for anion recognition . Indeed, its strength and strong directionality have led to its wide use in materials design and crystal engineering − and have found more recent applications in the solution phase for anion recognition, transport and sensing, or organocatalysis. − Although the XB-anion receptors display a large range of various structures, from acyclic compounds to interlocked molecules, − the XB motifs used are still mainly limited to neutral or cationic hetero- or carbocycles (e.g., haloperfluoroarene, halotriazole, halotriazolium, haloimidazolium, and halopyridinium motifs). These XB donors are based on halogen atoms bounded to carbon atoms included in an aromatic cycle, inhibiting a possible nucleophilic substitution that could occur on aliphatic ones, in the presence of anions.…”

“…The steric hindrance of the isobutyl groups might account for the more elongated transannular distance and the specific conformation of the atrane structure in 1b-Cl + •PF 6 − . These structural features are also probably retained in solution, which could account for the peculiar 31 P NMR chemical shift observed for 1b-Cl + •PF 6 − . Anion Binding Properties.…”

Modulation of the electronic states and magnetic properties of nickel catecholdithiolene complex by oxidation-coupled deprotonation

“…The construction of such a 3D framework based on the metal dithiolene complex has been limited to a few examples of crystals consisting of a gold catecholdithiolene complex in our previous work 44 and metal iodothiazoledithiolene complexes. 54 With regard to the molecular structures of the nickel complex in this crystal, the C-O and C-S bond lengths are almost the same as those of the Ni complex in 2-Ni and the [Au(catdt) 2 ] À complex 44 (Table 1). This indicates that the hydroxy groups of the nickel complex in this crystal are not deprotonated (Fig.…”

The quest for single component molecular metals within neutral transition metal complexes

“…The last member of this [M(RS-tzdt) 2 ] family is [Au(I-tzdt) 2 ] (I-tzdt: 2-iodo-1,3-thiazole-4,5-dithiolate, Chart 3), that as a compressed pellet, displays a s RT of 4-5 Â 10 À3 S cm À1 . 83 In this thiazole family, and as in the thiophene/selenophene the molecular system is very sensitive to the introduction of bulkier substituent groups, precluding in some cases the molecular interactions, affecting the transport properties. The molecular interactions in these cases may also be affected by open/close shell nature of the central TM, since the number of electrons in the molecule may condition the molecular overlapping modes.…”