Reactions of heterobimetallic 3d-4f Schiff base complexes of the formula [ZnLnL(H(2)O)(NO(3))(3)] (1a-e) with KOCN or NH(4)SCN in refluxing MeCN produce either one dimensional polymeric materials [ZnLnL(NO(3))(2)(H(2)O)(OCN)](infinity) (2a-c) or trinuclear complexes of the formula [Zn(2)LnL(2)(NO(3))(SCN)(2)] (3a-e) (a (La), b (Nd), c (Er), d (Tb), e (Eu); H(2)L = N,N'-bis-(3-methoxysalicylidene)ethylene-1,2-diamine). The structures of 2a,b and 3b-e have been determined by single-crystal X-ray diffraction studies. Structural differences between the complexes affect the photophysical properties, which have been studied in acetonitrile solutions.