One of the challenging topics of modern material science is the creation of functional microporous materials based upon metal-organic frameworks. The key task to aim this is the rational design and synthesis of suitable building blocks for the intelligent construction of coordination polymers with target properties. Pyridazine functionalized adamantanes (L1 and L2) were employed as a new class of geometrically rigid polydentate ligands to reach coordination polymers of programmed structure. The inflexible geometry and the presence of four nodal positions in adamantane allow the modification of this core by donor groups with a fixed direction of coordination. These ligands have a tendency to back-bonding related to the presence of electron-poor aromatic cycles and, thereby, enhanced affinity to the soft Lewis acids (Cu+ , Ag+ ). Such coordination results in various polynuclear motifs [Men(pdz)m] organized in 2D and 3D structures that were studied by x-ray diffraction. Going into details, the crystal structure of terephthalate complex of L1 is formed of binuclear units [Ag2(µ-pdz)(µ2-pdz)] connected by pyridazine and carboxylate bridges in 2D framework (1). On the other hand, the presence of third pyridazine cycle in L2 induces the linking of clusters [Ag4(2-pdz)6] into 3D coordination polymer [Ag4(L2)3(1,4- C6H4(COО)2)2·H2O] (2) (Fig. 1). In the case of halide complexes [Cu7I7(L1)2] (3) and [Cu6I6(L2)2]∙H2O (4) the formation of more complicated polynuclear motifs is observed due to the increased affinity of the anion to copper (I) ions. Relations between the number of donating groups and the dimensionality of compounds formed were depicted also for cyanide complexes [Cu2(CN)2(L1)] (5) and [Cu4(CN)4(L2)]∙H2O (6). Their 2D and 3D structures were formed by linking (Сu ICN)n chains with µ2-L1 and µ4-L2 pyridazine bridges. After all, the nature of the anion can be also a crucial factor in formation of the structure: a complex of L1 with a longer dicyanoamide bridge exists as 3D porous framework [Cu2(N(CN)2)2(L1)]·CHCl3 (7) (Fig.2).Fig.1. Fragment of 2 showing linking of the silver/pyridazine double chains by hexadentate ligand moleculesFig. 2. Porous structure of 7 formed through the bridging of (Cu[N(CN)2])n chains by L1