Synthesis, Crystal Structures, Magnetic Properties and Photoconductivity of C 60 and C 70 Complexes with Metal Dialkyldithiocarbamates M(R 2 dtc) 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 n Pr

New complexes of fullerenes C 60 and C 70 with metal dialkyldithiocarbamates, [M(R 2 dtc) x ] · [C 60 ( 70 )] · [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 = n Pr [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 (NCS 2 ) 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 10 3 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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)