In order to evaluate the impact of bridge conformation on electronic coupling in donor-bridge-acceptor triad systems, two Mo-2 dimers, [Mo-2(DAniF)(3)](2)[mu-1,4-{C(O)-NH}(2)-Naph] (1, DAniF = N,N'-di(p-anisyl)formamidinate and Naph = naphthalenyl) and [Mo-2(DAniF)(3)](2)[mu-1,4-(CS2)(2)-2,5-Me2C6H2] (2), have been synthesized and structurally characterized. These two compounds feature a large dihedral angle (>60 degrees) between the central aromatic ring and the plane defined by the Mo-Mo bond vectors, which is distinct from the previously reported phenylene bridged analogues [Mo-2(DAniF)(3)](2)[mu-1,4-{C(O)NH}(2)-ph] (I) and [Mo-2(DArliF)(3)](2)[mu-1,4-(CS2)(2)-C6H4] (II), respectively. Unusual optical behaviors are observed for the mixed-valence (MV) species (1(+) and 2(+)), generated by single-electron oxidation. While 2(+) exhibits a weak intervalence charge transfer (IVCT) absorption band in the near-IR region, the IVCT band is absent in the spectrum of 1+, which is quite different from what observed for I+ and II+. Optical analyses, based on superexchange formalism and Hush model, indicate that, in terms of Robin Day classification, mixed-valence species It belongs to the electronically uncoupled Class I and complex 2(+), with H-ab = 220 cm(-1), is assigned to the weakly coupled Class II. Together with I+ and II+, the four MV complexes complete a transition from Class I to Class II-III borderline as a result of manipulating the geometric topology of the bridge. Given the structural and electronic features for the molecular systems, the impacts of electrostatic interaction (through-space) and electron resonance (through-bond) on electronic coupling are discussed.