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

Abstract

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

Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2

“…A noteworthy observation is that 1, which is thermodynamically unstable with "genuine SI" 2, can be maintained in the presence of MeCN. In summary, the above observations are consistent with the overall preferential formation of dimeric 2 and 7, a result consistent with the literature precedents which overwhelmingly adopt the dimeric motif [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49].…”

“…4b, i.e. being the common structural motif for molecules of the general formula {Cd[S2CNRRꞌ]2}2 [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49]. In this structure the S1-and S3 dithiocarbamate ligands are κ 2 -chelating and µ2κ…”

“…2 -tridentate dithiocarbamate ligands leading to penta-coordinate geometries, regardless of whether the R groups were the same [31][32][33][34][35][36][37][38][39][40][41][42][43][44], dissimilar [39,45], incorporated within a cyclic system [46][47][48][49], or whether the compound was co-crystallised with another species [35,39,47], or that the R group carried additional potential oxygen donor atoms [44,49]. However, this situation changed in 2013 with the report of a coordination polymer, [{Cd[S2CN(iPr)CH2CH2OH]2}3·MeCN]∞ [50].…”

Serendipitous compositional and structural diversity in urotropine adducts of binary cadmium xanthates

“…2 -tridentate [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34]. This dramatic difference in structural outcomes is rationalised in terms of the significant contribution of the canonical structure shown in Fig.…”

“…In the crystal packing, molecules self-assemble into a supramolecular layer in the ab-plane being connected by C-H The structures of one-dimensional, zigzag coordination polymers 1 and 2 complement the sole previous example of a linear coordination polymer constructed from Cd(S2COiPr)2 and a bridging 4,4ꞌ-bipyridine ligand, [Cd(S2COiPr)2(4,4ꞌ-bipy)]n [46]. The zero-dimensional aggregate seen in 3 has only one precedent in the literature, namely in the structure of [{Cd(S2COEt)2}2L2], where L is the S-bound thiourea derivative, bis(4-methoxyphenyl)thiourea [78] but resembles the almost universally adopted structural motif adopted by binary cadmium dithiocarbamates [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34]. As revealed in the previously mentioned review of the inverse coordination propensities of hmta in non-silver containing coordination polymers [67], µ2-, µ4-and µ4-bridging modes have been observed but terminally bound examples are comparatively rare in this context.…”