Stereochemical geometries and photoluminescence in pseudo‐halido‐zinc(Ii) complexes. structural comparison between the corresponding cadmium(ii) analogs

Six pseudohalide zinc(II) containing a variety of N‐donor auxiliary amines were structurally characterized. These include two mononuclear trigonal bipyramidal [Zn(NTB)(N3)]ClO4∙½H2O (3) and [Zn(TPA)(NCS)]ClO4 (4), two distorted octahedral [Zn(1,8‐damnph)2(dca)2] (5) and [Zn(8‐ amq)2(dca)2] (6a) as well as two 1D polymeric chains catena‐[Zn(isq)2(μ1,5‐dca)2] (7) and catena‐ [Zn(N,N‐Me2en)2(μ1,5‐dca)]dca (8), where NTB = tris(2‐benzimidazolylmethyl)amine, TPA = tris(2‐ pyridylmethyl)amine, 1,8‐damnph = 1,8‐diaminonaphthalene, 8‐amq = 8‐amino‐quinoline, isq = isoquinoline (isq) and N,N‐Me2en = N,N‐dimethylethylenediamine. In general, with the exception of 6 and 8, the complexes exhibited luminescence emission in MeOH associated with red shift of the emission maxima, and the strongest visible fluorescence peak was detected at 421 nm (λex = 330 nm) in the case of Complex 5.