The complex formation of members of the so-called chiragen ligand family (stereoselective linked bis-[4,5]-pineno-2,2'-bipyridines) with Cd(II), Zn(II) and Fe(II) was investigated. Using spectrophotometric titrations and electrospray MS it was determined that the major species formed in solution are complexes with an M:L=2:3 stoichiometry. Based on circular dichroism (CD) and NMR measurements, a triple-helical structure with enantiomerically pure homochiral configuration at the metal centers is proposed for these dinuclear complexes. This is one of the first examples of a spontaneous self-assembly process leading to a dinuclear triple-helicate with pronouced preference for the formation of one of the possible stereoisomers.