Vapor diffusion of diethyl ether into a methanol/dichloromethane (v/v, 1:1) solution of M(NO 3 ) 2 (M=Cd 2 + , Co 2 + , Zn 2 + ) and the site-differentiated solvated cluster trans-[Re 6 (μ 3 -Se) 8 (PEt 3 ) 4 (4,4 ' -dipyridyl) 2 ](SbF 6 ) 2 afforded supramolecular arrays featuring the [Re 6 (μ 3 -Se) 8 ] 2 + core-containing clusters mediated by the transition metal ions. The cluster complex with two 4,4 ' -dipyridyl moieties can be viewed as an expanded dipyridyl ligand, serving to coordinate the transition metal ions via a pair of N p y r i d y l -M dative bonds. All compounds have been characterized by microanalysis (CHN) and their solid-state structures have been established by single crystal X-ray diffraction. Two polymorphous forms (1 and 2) of the crystal of M Cd 2 + have been obtained, one of which (1) exhibits a highly porous structure, whereas the other (2) displays a wavy one-dimensional arrangement. The latter form is isostructural with the complex with Co 2 + (3). In the case of Zn 2 + (4), the cluster complex ligand and the mediating Zn 2 + are arranged in a zigzag fashion, with an average N p y r i d y l -M-N p y r i d y l angle bond of 88 o .