In this paper, we describe the extremely unusual optical properties of Rull-based electron donor-acceptor (D-A) polyene and some closely related chromophores. For three different polyene series, the intense, visible d-->pi* metal-to-ligand charge-transfer bands unexpectedly blue-shift as the number of E-ethylene units (n) increases from 1 to 3, and the static first hyperpolarizabilities beta(0) determined via hyper-Rayleigh scattering and Stark spectroscopy maximize at n = 2, in marked contrast to other known D-A polyenes in which beta(0) increases steadily with n. Time-dependent density-functional theory and finite field calculations verify these empirical trends, which arise from the orbital structures of the complexes. This study illustrates that transition metal-based nonlinear optical chromophores can show very different behavior when compared with their more thoroughly studied purely organic counterparts.