SYNTHESIS AND SPECTROSCOPICAL PROPERTIES OF DI(PHTHALOCYANINATO(1-))LANTHANIDEPOLYBROMIDE - CRYSTAL-STRUCTURE OF ALPHA-DI(PHTHALOCYANINATO)SAMARIUMPOLYBROMIDE ALPHA-[SM(PC)(2)]BR-1.45 AND ALPHA-DI(PHTHALOCYANINATO)SAMARIUMPERCHLORATE, ALPHA-[SM(PC)(2)](CLO4)(0.63)

Bronze-coloured di(phthalocyaninato)lanthanidepolybromide, [Ln(Pc(-))( 2)]Br-y (Ln = La...(-Ce, Pm)...Lu; y > 1.5) is prepared by oxidation o f ((n)Bu(4)N)[Ln(Pc(2-))(2)] with bromine in excess. The UV-VIS-NIR sp ectra show the typical B and Q(1) bands of the Pc(-) ligand at similar to 14 kK and similar to 20 kK. For the [Ln(Pc(-))(2)](+) cation a NIR (D) band between 9,14 kK (La) and 11,50 kK (Lu) is characteristic for dimeric cofacial Pc(-) radicals. Within the row La...Lu, there is a li near relationship of the hypsochromic shift of the strong bands and th e Ln(III) radius. In the case of La-Nd the D band shifts successively with longer time of bromination to similar to 3 kK as a result of incr easing electron delocalisation. Characteristic vibrational bands are a t similar to 1350/1450 cm(-1) (IR) and similar to 560/1120/1170/1600 c m(-1) (RR). In the FT-Raman spectra the totally symmetric Ln-N stretch ing vibration between 141 cm(-1) (La) and 172 cm(-1) (Lu) is selctivel y enhanced. As shown by alpha-[Sm(Pc)(2)]Br-1,Br-45 and alpha-[Sm(Pc)( 2)](ClO4)(0,63) only partially ringoxidized complexes are obtained by the anodic oxidation. Both crystallize in the tetragonal space group P 4/nnc. The [Sm(Pc)(2)] molecular building block contains two nearly pl anar staggered (similar to 41 degrees) Pc rings packed in columns para llel along [001] leading to the quasi-one-dimensional structure. There is a statistical disorder of the Sm-III and the ClO4- resp. Br-/Br-3( -) ions over two incompletely filled crystallographic positions for th e cation resp. anion. This results in a partial oxidation of the Pc li gand, which in the picture of localized valence states for alpha-[Sm(P c)(2)](ClO4)(0,63) corresponds to [SmPc(-)Pc(2-)] . 2[Sm(Pc(-))(2)](Cl O4). Accepting the same valence state for [Sm(Pc)(2)]Br-1,Br-45 five p ositive charges are compensated by two Br- and three Br-3(-). The spec troscopic differences of the partially and fully oxidized complexes ar e discussed.