Fullerene complexes with divalent metal dithiocarbamates: structures, magnetic properties, and photoconductivity

Abstract

A series of complexes of fullerenes C60 and C70 with metal dithiocarbamates {MII(R2dtc)2}·Cm (m = 60 or 70) and metal dithiocarbamates coordinated to nitrogen-containing ligands (L), {MII(R2dtc)2)x·L}·C60 (x = 1 or 2), where M = Cu, Zn, Cd, Hg, Mn, or Fe, R = Me, Et, Prn, Pri, or Bun, L is 1,4-diazabicyclo[2.2.2]octane (DABCO), N,N′-dimethylpiperazine, or hexamethylenetetramine, were synthesized. The shape of dithiocarbamate molecules is sterically compatible with the spherical shape of C60, resulting in an efficient interaction between their π systems. The resulting compounds are characterized by a layered or three-dimensional packing of the fullerene molecules. In the C60 complexes, iron(II) and manganese(II) dithiocarbamates exist in the high-spin states (S = 2 and 5/2). The magnetic susceptibility of {MII(Et2dtc)2}2·Cm (M = Fe or Mn, m = 60 or 70) in the temperature range of 200–300 K is described by the Curie-Weiss law with Θ = −250 and −96 K and with maxima at 110 and 46 K, respectively, which is indicative of a strong antiferromagnetic spin coupling between MII. The Weiss constants for the [{MII(Et2dtc)2}2·DABCO]·C60·(DABCO)2 complexes (M = Fe or Mn) are 1.7 and 0.3 K, respectively. The magnetic moments of the complexes containing Fe and Mn dithiocarbamates slightly increase at temperatures below 50 and 35 K, respectively, which is evidence of the ferromagnetic spin coupling between MII in {MII(Et2dtc)2}2·DABCO. Single crystals of the complexes exhibit low dark conductivity (10−10–10−11 S cm−1). The visible light irradiation of these crystals leads to an increase in the photocurrent by two–three orders of magnitude. The photogeneration of free charge carriers in the complexes occurs both due to the photoexcitation of metal dithiocarbamate (CuII(Et2dtc)2) and through the charge transfer from metal dithiocarbamate (MII(Et2dtc)2, M = Zn or Cd) to C60.