A dissymmetric 1,10-phenanthroline chelate (N-phen-S) bearing two polyether chains terminated by two monodentate ligands of the benzonitrile (N) and dialkylesulfoxide (S) types was synthesized, characterized, and coordinated to ruthenium. The corresponding Ru(terpy)(N-phen-S)2+ complexes (terpy = 4'-(3,5-ditertiobutylphenyl)-2,2';6',2' '-terpyridine) were fully characterized as being two coordination isomers of the scorpionate type with one of the two tails occupying the sixth position on the coordination sphere. Photoexpulsion of the coordinated tail led to opening of the ruthena-macrocycle and subsequent rearrangement of the bidentate chelate. This rearrangement consisted of a 90 degrees rotation of the phenanthroline around the ruthenium atom. Selective irradiation of one isomer in a mixture of the two was undertaken using band-pass filters; this resulted in an enrichment of the nonirradiated isomer in the mixture. Thermal back-coordination of the tail was investigated in the dark. It took place quantitatively from the corresponding ruthenium chloride complex by trapping of the anion with silver salts.