Supramolecular approach to the synthesis of [60]fullerene-metal dithiocarbamate complexes, {(M^II(R₂dtc)₂) _x· L}·C₆₀ (M = Zn, Cd, Hg, Fe, and Mn; x = 1 and 2). The study of magnetic properties and photoconductivity

Coordination assemblies formed by metal(II) dithiocarbamates M ^II(R₂dtc)₂ (M = Zn, Cd, Hg, Mn, and Fe; R = Me, Et, iPr, nPr, and nBu) and nitrogen-containing ligands (L = DABCO, DMP, and HMTA) are shown to be sterically well consistent with the spherical shape of fullerenes and are effectively cocrystallized with them to form complexes {(M^II(R²dtc)₂)_x·L} ·C₆₀ (x = 1 and 2) with layered or three-dimensional (3D) packing of fullerene molecules (1-11). For the first time the molecular structures of the M^II(R2dtc)₂ assemblies in the complexes with C₆₀ are presented (including those with M = Mn, Fe, and Hg). According to optical and electron paramagnetic resonance (EPR) spectroscopy 1-11 have a neutral ground state. Magnetic susceptibilities of {[M ^II(Et₂dtc)₂]₂· DABCO}·C₆₀-(DABCO)₂ (M = Mn and Fe) follow the Curie-Weiss law in the 50-300 K range with the Weiss constants θ = 0.35 and 1.70 K, respectively. Magnetic moments of the complexes equal to 8.23 and 6.88 μ_B at 300 K correspond to the high-spin state of the Mn ^II (S = 5/2) and Fe^II (S = 2) ions. The increase of μ_eff observed below 35 and 50 K up to 8.5 μ_B (at 3 K) and 7.4 μ_B (at 6 K) indicates the manifestation of short-range ferromagnetic interactions between Mu spins in the isolated [M ^II(Et₂dtc)₂]₂· DABCO dimers. Under illumination by white light, the complexes show up to 10² times increase of photocurrent. The main contribution to the generation of free charge carriers is provided by direct charge transfer from {M ^II(R2dtc)₂}₂·L to C₆₀. It was found that photocurrent increases in magnetic field with induction B < 1 T.