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The oxygen-evolving complex (OEC) is the native enzyme that catalyzes the oxidation of water in natural photosynthesis. Two new classes of manganese cluster complexes of formula Ba2Mn2L12(H3L1)2(CH3OH)4 1 and Mn4L26Cl2 2 were prepared (H4L1 = N,N′-(ethane-1,2-diyl)bis(2-hydroxybenzamide); L2 = methyl picolinimidate) and characterized by standard techniques including microanalysis, IR spectroscopy, ESI spectrometry, and magnetic susceptibility measurements. X-ray diffraction studies of these complexes revealed (i) a box-type structure for 1 formed by two redox-active manganese(III) ions and two barium(II) ions connected by two bridging bisamido-bisphenoxy ligand molecules; and (ii) a planar-diamond array for Mn4N6 cluster 2 where the picolinimidates act as chelating ligands through the two nitrogen atoms. The ability of 1 and 2 to split water has been studied by means of water photolysis experiments. In these experiments, the oxygen evolution was measured in aqueous media in the presence of p-benzoquinone (acting as the hydrogen acceptor), the reduction of which was followed by UV-spectroscopy. The relevant photolytic activity found for 1 is in contrast to the inactivity of 2 in the photolytic experiments. This different behavior is discussed on the basis of the structure of the biomimetic models and the proposed reaction mechanism for this process supported by DFT calculations.