Substituent and isomer effects on the structural, spectroscopic, (UV-visible and ESR) and electrochemical properties of dirhodium(III,II) 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)(2,4,6-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)(C triple bond C)(2)Si(CH(3))(3) are also reported and the data on these compounds is discussed in light of their parent complexes, (3,1) Rh(2)(2,6-F(2)ap)(4)Cl and (4,0) Rh(2)(2,4,6-F(3)ap)(4)Cl.