New molecular complexes of fullerenes C-60 and C-70 with tetraphenylporphyrins M(tpp) , in which M = H-2, Mn, Co, Cu, Zn, and FeCl

New molecular complexes of fullerenes C-60 and C-70 with tetraphenyl-porphyrins [M(tpp)] in which M = H-2, Mn-II, Co-II, Cu-II, Zn-II and (FeCl)-Cl-III, have been synthesised. Crystal structures of two C-60 complexes with H2TPP, which differ only in the number of benzene solvated molecules, and C-60 and C-70 complexes with [Cu(tpp)] have been studied. The fullerene molecules form a honeycomb motif in H2TPP . 2C(60). 3C(6)H(6), puckcred graphite-like layers in H2TPP . 2C(60). 4C(6)H(6), zigzag chains in [Cu(tpp)].C-70.1.5C(7)H(8).0.5C(2)HCl(3) and columns in [Cu(tpp)](2).C-60. H2TPP has van der Waals contacts with C-60 through nitrogen atoms and phenyl groups. Copper atoms of the [Cu(tpp)l molecules are weakly coordinated with C- 70, but form no shortened contacts with C-60. The formation of molecular complexes with fullerenes affects the ESR spectra of [M(tpp)] (M = Mn, Co and Cu). [Mn(tpp)] in the complex with C- 70 lowers its spin state from S = 5/2 to S = 1/2, whereas [Co(tpp)] and [Cu(tpp)] change the constants of hyperfine interaction. ESR, IR, UV-visible and X-ray photoelectron spectroscopic data show no noticeable charge transfer from the porphyrinate to the fullerene molecules

sp2 amorphous carbons in view of multianalytical consideration: Normal, expeсted and new

sp2 Amorphous carbons are considered as objects of the modern nanotechnology. A particular set of the highest‑carbon-content sp2 species, two natural amorphous carbons (shungite carbon and antraxolite) as well as two engineered carbon blacks were subjected to analytical study by using a set of selected modern structural and compositional analytical techniques. The suggested approach occurred quite efficient and allowed disclosing a number of steady points that are common to the whole class of this carbon allotrope and are able to get a vision of atom-molecular representation of the solids. Among the commonalities observed, there are the following: i) sp2 Amorphous carbons are conglomerates of nanographites, basic structure units of which lay the foundation of the atom-molecular description of the solids. ii) The units represent framed graphene molecules of 1÷2 nm and of 1÷ (1÷3)*10 nm in size in the case of natural and engineered products, respectively. iii) The molecule framing, predominantly incomplete with respect to the number of vacant places, concerns only edge atoms and is implemented by the related chemical additives, such as hydrogen, oxygen, nitrogen, sulfur and halogens which are attached to the carbon core via chemical bonding. iv) Inelastic neutron scattering and X-ray photoelectron spectroscopy allow attributing the bonds to chemical compositions involving hydrogen and oxygen while quantum chemistry ensures reliable support. v) The basic structure units of sp2amorphous carbons are strongly radicalized due to which the latter acquire new properties, being the largest repository of stable radicals. © 2019 Elsevier B.V