Ionic complexes simultaneously containing fullerene anions and coordination structures of metal phthalocyanines with I− and EtS− anions (original) (raw)

2011, Russian Chemical Bulletin

The ionic complexes simultaneously containing negatively charged coordination structures of metal phthalocyanines and fullerene anions, viz., {Mn II Pc(CH 3 CH 2 S-) x •(I-) 1-x }•(C 60 •-)• •(PMDAE +) 2 •C 6 H 4 Cl 2 (PMDAE is N,N,N´,N´,N´ pentamethyldiaminoethane, x = 0.87, 1) and {Zn II Pc(CH 3 CH 2 S-) у •(I-) 1-y } 2 •(C 60-) 2 •(PMDAE +) 4 •(C 6 H 4 Cl 2) (y = 0.5, 2) were syn thesized. The both compounds were obtained as single crystals, which made it possible to study their crystal structures. In complex 1, the fullerene radical anions form honeycomb like layers in which each fullerene has three neighbors with center to center interfullerene distances of 10.13-10.29 Å. Rather long distances between the C 60 •-radical anions results in the retention of monomeric C 60 •-in this complex down to the temperature of 110(2) K. In complex 2, fullerenes form dimers (C 60-) 2 bonded by one CC bond. The dimers are packed in corrugated honeycomb like layers with interfullerene center to center distances of 9.90-10.11 Å. Manganese(II) and zinc(II) phthalocyanines coordinate iodide and ethanethiolate anions to the central metal atom to form unusual negatively charged coordination structures M II Pc(An-) (Anis anion) packed in dimers {M II Pc(An-)} 2 with a short distance between the phthalo cyanine planes (3.14 Å in 1 and 3.27 Å in 2). The pthalocyanine dimers also form layers with the PMDAE + cations, and these layers alternate with the fullerene layers. The packing of spherical fullerenes with planar phthalocyanine molecules is attained by the insertion of fullerenes between the phenylene groups of phthalocyanines. The π-π interactions of the porphyrin macrocycle with five or six membered fullerene rings are characteristic of the earlier studied ionic porphy rin and fullerene complexes. Such interactions are not observed for ionic complexes 1 and 2. Key words: fullerene С 60 , manganese(II) and zinc(II) phthalocyanines, crystal structure, dimerization of C 60 •-, coordination of anions with metal phthalocyanines.