Synthesis, crystal structures, magnetic properties and photoconductivity of C60 and C70 complexes with metal dialkyldithiocarbamates M(R2dtc)x, where M = CuII, CuI, AgI, ZnII, CdII, HgII, MuII, NiII, and PtII;: R = Me, Et, and nPr

New complexes of fullerenes C-60 and C-70 with metal dialkyldithiocarbamates, [M(R(2)dtc)(x)]center dot[C-60((70))]center dot[Solvent], R = Et [M = Cu-II (C-60, 1; C-70, 2), Cu-I(C-60, 3; C-70, 4), Ag-I (C-60, 5), Zn-II (C-60, 6), Cd-II (C-60, 7; C-70, 8), Hg-II (C-60, 9), Mn-II (C-70, 10)], R = Et and Me [M = Cu-II (C-60, 11), and Zn-II (C-60, 12)], and R = nPr [M = Cu-II (C-60, 13), Ni-II (C-60, 14), and Pt-II (C-60, 15)] were obtained. M(R(2)dtc)(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(2)dtc)(2) because of a weak coordination of Cu-II to fullerene and a flattening of the central (NCS2)(2)CU 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(Et(2)dtc)(2)](2) dimers in 10. The illumination of the crystals of 1, 2, and 7 by white light results in up to a 101 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(Et(2)dtc)(2) in 1 and 2, and by charge transfer from Cd(Et(2)dtc)(2) to C-60 molecules in 7. The decrease of photocurrent in 1 and 7 in a weak magnetic field with B-0 < 0.5 T was found. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)