Experimental and Theoretical Evidence of π‐d Interactions in Supramolecular Assemblies Based on TTF‐CH=CH‐Py Ligands Tethered to Mo₆Xⁱ₈ Octahedral Molybdenum Halide Cluster Cores

Abstract

Abstract Synthesis, characterization, and physical properties of [Mo 6 X i 8 (TTF‐CH=CH‐Py) a 6 ] 4+ supramolecular assemblies [TTF = tetrathiafulvalene; Py = pyridine; X = Cl ( 1 ), Br ( 2 ),I ( 3 )] resulting from the reaction between [Mo 6 X i 8 (OSO 2 CF 3 ) 6 ] 2– cluster precursor and TTF‐CH=CH‐Py ligands were investigated. They are based on the association of the strongly delocalized metallic electron [Mo 6 X i 8 ] 4+ cluster cores with six redox‐active π‐conjugated TTF‐CH=CH‐Py terminal ligands attached to the Mo clusters through the pyridinyl group. Synergetic π‐d interactions between the organic ligands and the cluster core were experimentally evidenced by electrochemistry and absorption measurements, and corroborated by DFT calculations.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)