Abstract
Two new tetranuclear \(\{\text{Mn}_{2}^{\text{II}}\text{Mn}_{2}^{\text{III}}\}\) clusters are obtained and studied by single crystal X-ray diffraction. They have similar coordination motifs involving p-H-calix[4]arene HCA or p-adamantylcalix[4]arene AdCA and 2,2′-bipyrimidine as N,N-donor chelating coligand. Two factors affecting the controlled cluster core deformation are revealed: the involvement of 2,2′-bipyrimidine in coordination with Mn(II) ions decreases the MnII–MnII distance; the introduction of bulky p-adamantyl groups along the calix[4]arene upper rim increases the MnIII–MnIII distance. Moreover, the presence of bulky substituents at the macrocycle platform is shown to change the molecular arrangement in the crystal, which leads to the formation of a porous crystal structure.
