The large bridging ligand 9,10-anthracenedicarboxylate and its thiolated derivatives have been employed to assemble two dimolybdenum complex units and develop three Mo-2 dimers, [Mo-2(DAniF)(3)](2)(mu-9,10-O-2 CC14H8CO2), [Mo-2(DAniF)(3)](2)(mu-9,10-OSCC14H8COS), and [Mo-2(DAniF)(3)](2) (mu-9,10-S-2 CC14H8CS2) (DAniF = N,N'-di(p-anisyl)formamidinate), for the study of conformation dependence of the electronic coupling between the two Mo-2 centers. These compounds feature a large . deviation of the central anthracene ring from the plane defined by the Mo-Mo bond vectors, with the torsion angles (phi = 50-76 degrees) increasing as the chelating atoms of the bridging ligand vary from O to S. Consequently, the corresponding mixed-valence complexes do not exhibit characteristic intervalence charge transfer absorptions in the near-IR spectra, in contrast to the phenylene and naphthalene analogues, from which these systems are assigned to the Class I in Robin-Day's scheme. Together with the phenylene and naphthalene series, the nine total mixed-valence complexes in three series complete a transition from the electronically uncoupled Class Ito the strongly coupled Class II-HI borderline via moderately coupled Class II and permit a systematic mapping of the bridge conformation effects on electronic coupling. Density functional theory calculations show that the HOMO-LUMO energy gap, corresponding to the metal (delta) to ligand (pi*) transition energy, and the magnitude of HOMO-HOMO-1 splitting in energy are linearly related to cos(2) phi. Therefore, our experimental and theoretical results concur to indicate that the coupling strength decreases in the order of the bridging units: phenylene > naphthalene > anthracene, which verifies the through-bond superexchange mechanism for electronic coupling and electron transfer.