New organobimetallic Mo/Fe compounds of the type [Mo(Tp(An))(NO)(Cl)(Y-pi-bridge)(Fc)] {Tp(An) = hydrotris-(3-p-methoxyphenylpyrazol-1-yl)borate; Fc = (eta(5)-C5H4)Fe(eta(5)-C5H5); Y = NH (1), O (5), bridge = C6H4; Y NH, bridge C6H3R-N=N-C6H3R＇ [R = R＇ H (2); R = CH3, R＇ = H (3); R = R＇ = CH3 (4); Y = NH, bridge = C6H4-CH=CH-C6H4 (6)} have been synthesized and characterized. The second-harmonic generation yield of corona-poled spin-coated films of poly(methyl methacrylate) containing these compounds has been investigated. The three nonzero components, chi(31)((2)), chi(15)((2)), and chi(33)((2)), of the susceptibility tensor have been measured. chi 31(2) is the highest component at different with linear (one-dimensional) molecules where chi(33)((2)) = 3 chi(31)((2)) Moreover, Kleinman symmetry (chi(31)((2)) = chi(15)((2)) is not obeyed. These results have been discussed on the basis of a low-lying charge-transfer optical transition that has a perpendicular component to the permanent dipole moment. From the measured chi((2)) components, the molecular hyperpolarizabilities beta(33), beta(15), and beta(31) have been estimated under the assumption of thermal equilibrium under the poling field. On the ether hand, the role of diverse bridging structures on the susceptibilities, including different lengths (diarylazoamide vs anilide), as well as methyl substituents and linking (C-C vs N=N) groups, has been evaluated. Moreover, the acceptor [Mo(Tp(An))(NO)(Cl)(Y)] and nitro groups have been compared in compounds having the same ferrocenyl donor group and polarizable bridging system. chi(31)((2)) susceptibilities are significant in most cases, and values as high as 6.6 x 10(-9) esu have been obtained for the 4-nitro-4＇-ferrocenylstilbene compound.