Formation of μ2-hydroxo-bonded (MgPc)2OH− assemblies and (C60−)2 dimers in ionic fullerene {(MgPc)2OH−}2·(C60−)2·(cation+)4 complexes

摘要: Ionic complexes containing μ2-hydroxo-bonded (MgPc)2OH− phthalocyanine assemblies and C60− anions: {(MgPc)2OH−}2·(C60−)2·(PMDAE+)4·(C6H5CN)4 (1); {(MgPc)2OH−}2·(C60−)2·(TMP+)4·(C6H5CN)3·(C6H4Cl2)2.5 (2) (where PMDAE+ is the cation of N,N,N′,N′,N′-pentamethyldiaminoethane TMP+ N,N′N′-trimethylpiperazinium cation) have been obtained as single crystals. The ionic ground state justified by EPR spectra in IR NIR ranges. C60˙− radical anions are dimerized both 1 2 240–220 K range. Dimerization accompanied reversible transition from paramagnetic to diamagnetic state. MgPc forms unusual assemblies, which hydroxo-anion coordinates two molecules a μ2-fashion. length Mg–O bonds 1.936–1.955(2) A, Mg–O–Mg angle 133.37–135.27(4)° displacement Mg atoms out mean 24-atom plane 0.77–0.86 A. packing spherical fullerene planar attained crystal insertion fullerenes between phenylene groups phthalocyanines. It has shown that metal phthalocyanines with C60 form MIIPc·(L−) whereas metalloporphyrins MIIporphyrin·(C+) assemblies.