Given the fact that the chemical composition and crystal structure of a compound define its properties, a thorough understanding of the factors that allow for the realization of a certain combination of elements is an essential point when designing new applicable materials. In the case of intermetallic compounds, however, the composition-structure-property relationships are often poorly understood. Complex structural chemistry of such polar intermetallics is caused by an interplay between covalent, metallic, and ionic interactions. The discovery of high-temperature superconductivity in iron-pnictides has sparked enormous interest in intermetallic compounds containing square-planar lattice arrangement of transition metal atoms, particularly in ThCr2Si2-type representatives. It is known that the superconducting properties are very sensitive to the structural parameters of d-metal layers, and as such the structural flexibility for chemical substitution in ThCr2Si2-type materials makes this family of intermetallic compounds interesting candidates for studying the structure-property relationship. In this talk, the synthesis, structural features, and magnetic properties of new polar intermetallic compounds based on iron, cobalt, and nickel, with square-planar layers and other 2D-, 1D- and 3D- arrangements of transition metal atoms will be discussed.