Structural and Magnetic Properties of a Novel Ferrocenyl−Diiodine Charge Transfer Complex

Abstract

The reaction of 4-ferrocenyl-1,3-dithiole-2-thione with diiodine affords an unprecedented "double" charge-transfer complex; the highly ordered ferrocenium units are held by a supramolecular polyiodide chain, and the material shows evidence of the formation of zigzag magnetic chains below 2 K.

The role of functional nitro and cyano groups in the self‐assembly of 1,3‐dithiole‐2‐thione–halogen adducts

“…In this "free" diiodine molecule, the bond length is 2.736(5)Å. Although the inclusion of additional halogen molecules in polyhalide chains has been seen in other systems [6,[8][9][10], the remaining structures in this work are simple 1:1 adducts. The adduct 6.1.5IBr is isostructural to 6.1.5I 2 , with the thiocarbonyl sulfur coordinating to the iodine atom of the interhalogen and the occupancy of the bromine/iodine atoms of the free molecule in a random distribution.…”

“…For instance, the incorporation of ferrocene in 1 results in an open shell species with magnetic properties, due to the oxidation of the metallocene during adduct formation [6]. Functionalities that interact with the halogen adduct include esters (compound 2) via hydrogen bonding [8,9] and methylene bromide side groups (in 3) which form halogen-halogen contacts [10].…”

Diiodine complex of diferrocenyl(phenyl)phosphine sulfide: the structural and electrochemical behaviour of Fc2(Ph)PS·I2

“…We have recently reported the structural and magnetic properties of a remarkable ferrocenium-polyiodide charge-transfer complex 5, obtained by treating the parent ferrocene-substituted 1,3-dithiole-2-thione with diiodine. Rather than simply forming a molecular charge-transfer complex with the thiocarbonyl-sulfur, as one might have expected, the iron atom is simultaneously oxidised from Fe 2+ to Fe 3+ through a novel ÔdoubleÕ charge-transfer process [4]. The only previous report of simultaneous oxidation of the iron atoms and the heteroatoms in substituted ferrocenes was by Wei et al [5] with the formation of mixed valence Fe 2+ /Fe 3+ species.…”

Supramolecular polymers of 4,5-bis(bromomethyl)-1,3-dithiole-2-thione-dihalogen adducts

“…In such a case, stable open shell species may result with interesting electronic properties. For instance, we have isolated a 4-ferrocenyl-1,3-dithiole-2-thione-diiodine complex (1) showing antiferromagnetic properties 3 and a 1,3-dithiole-2thione charge transfer salt (2?I 2.5 ) with a conductivity of 1.2 6 10 24 S cm 21 . 4 Using different stoichiometries and reaction conditions, one can promote the formation of supramolecular structures in which the coordinated halogen species also interacts with additional 'free' dihalogen or interhalogen molecules to form polymeric chains.…”

“…4 Using different stoichiometries and reaction conditions, one can promote the formation of supramolecular structures in which the coordinated halogen species also interacts with additional 'free' dihalogen or interhalogen molecules to form polymeric chains. 3,5 The resulting materials often possess a high degree of order in the solid state, associated with an array of close intermolecular interactions; this type of arrangement is critical in fostering magnetic or conducting properties.…”