Substituent and isomer effects on the structural, spectroscopic, (UV-visible and ESR) and electrochemical properties of dirhodium(111,11) complexes containing four identical unsymmetrical bridging ligands are reported for seven related compounds of the type Rh-2(L)(4)Cl where L = 2-(2-fluoroanilino)pyridinate (2-Fap), 2-(2,6-difluoroanilino)pyridinate (2,6-F(2)ap), 2-(2,4,6-trifluoroanilino)pyridinate (2,4,6-F(3)ap), or 2-(2,3,4,5,6-pentafluoroanilino)pyridinate (F(5)ap) anion. Rh-2(2-FaP)(4)Cl exists only in a (4,0) isomeric conformation while Rh-2(2,6-F(2)aP)(4)Cl, Rh-2(214,6-F(3)ap)(4)Cl, and Rh-2(F(5)aP)(4)Cl exist as both (4,0) and (3,1) isomers. It had earlier been demonstrated that Rh-2(L)(4)Cl complexes can adopt different geometric conformations of the bridging ligands, but the current study provides the first example where two geometric isomers of Rh-2(5+) complexes are obtained for one compound using the same synthetic procedure. The synthesis, structural, spectroscopic, and/or electrochemical properties of (3,1) Rh-2(2,6-F(2)aP)(4)CN and (4,0) Rh-2(2,4,6-F(3)aP)(4)(CdropC)(2)Si(CH3)(3) are also reported and the data on these compounds is discussed in light of their parent complexes, (3,11) Rh-2(2,6-F(2)aP)(4)Cl and (4,0) Rh-2(2,4,6-F(3)aP)(4)Cl.