Synthesis, crystal structures, magnetic properties and photoconductivity of C₆₀ and C₇₀ complexes with metal dialkyldithiocarbamates M(R₂dtc)_x, where M = Cu^II, Cu^I, Ag^I, Zn^II, Cd^II, Hg^II, Mn ^II, Ni^II, and Pt^II; R = Me, Et, and nPr

New complexes of fullerenes C₆₀ and C₇₀ with metal dialkyldithiocarbamates, [M(R₂dtc)_x]·[C ₆₀(₇₀)]·[Solvent], R = Et [M = Cu^II (C₆₀, 1; C₇₀, 2), Cu^I (C₆₀, 3; C₇₀, 4), Ag^I (C₆₀, 5), Zn^II (C ₆₀, 6), Cd^II (C₆₀, 7; C₇₀, 8), Hg^II (C₆₀, 9), Mn^II (C₇₀, 10)], R = Et and Me [M = Cu^II (C₆₀, 11), and Zn^II (C ₆₀, 12)], and R = nPr [M = Cu^II (C₆₀, 13), Ni^II (C₆₀, 14), and Pt^II (C₆₀, 15)] were obtained. M(R₂dtc)_x efficiently cocrystallized with fullerene molecules as tetrahedral monomers (6, 12), dimers (1, 7, 11), and tetramers (3, 4). Fullerene molecules form closely packed hexagonal and square layers in 1, 7, and 11, hexagonal and tetragonal 3D structures in 6 and 12, and island motifs in 3 and 4. Complexes 1-15 have a neutral ground state. However, the formation of the complexes with fullerenes changes the environment of paramagnetic Cu^II and Mn^II. The EPR spectra of 1, 2, 11, and 13 are essentially modified relative to those of pristine Cu(R ₂dtc)₂ because of a weak coordination of Cu^II to fullerene and a flattening of the central (NCS₂)₂Cu fragments. Complex 10 shows a spectrum exhibiting features from 50 to 600 mT and manifests strong antiferromagnetic coupling of spins with a Weiss temperature of -96 K and the maximum of magnetic susceptibility at 46 K. Such magnetic behavior can be explained by the formation of [Mn(Et₂dtc) ₂]₂ dimers in 10. The illumination of the crystals of 1, 2, and 7 by white light results in up to a 10³ increase in photocurrent. The photoconductivity spectra have maxima at 470, 450-650, and 660 nm for 1, 2, and 7, respectively. Photogeneration of free charge carriers is realized by photoexcitation of Cu(Et₂dtc)₂ in 1 and 2, and by charge transfer from Cd(Et₂dtc)₂ to C₆₀ molecules in 7. The decrease of photocurrent in 1 and 7 in a weak magnetic field with B₀ < 0.5 T was found.