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In this work we have demonstrated the strategy toward hybrid materials that combine two photoactive components from different classes of compounds: octahedral iodide Mo(II) cluster (Mo6I8(Py)6) and zinc(II) or ruthenium(II) ditolyl-substituted A2-type porphyrinates ((ZnPor) and (Ru(CO)Por), correspondingly). Axial ligation of cluster pendant pyridyl ligands to metalloporphyrins leads to formation of Npy...M bonds (M = Zn(II), Ru(II)) and to assembling of unique organic-inorganic architectures. The structure and composition of the obtained cluster-porphyrin hybrids in solutions (CH2Cl2 or CHCl3) were investigated by 1H NMR including COSY and DOSY as well as UV-Vis spectroscopies. It was demonstrated that in the case of ZnPor molecules, the components participate in the rapid exchange due to the lability of Npy...Zn bonds, in contrast to solutions of RuPor(CO) where hybrid structures with different cluster/porphyrin ratio have been detected even in polar acetone.