Two hexadentate bipyridine ligands and their Ru-II and Ni-II complexes were prepared. The helical alignment of the three electron-donor-pi-bridge-electron-acceptor (D-pi-A) single-strands with bundle architecture in cooperation with the metal center can strongly enhance the nonlinear optical (NLO) properties. The complexation of the novel cage-type hexadentate ligands with a paramagnetic Ni-II-core almost doubles the beta(HRS) values compared with the corresponding diamagnetic Ru-II complexes. The hyper-Rayleigh scattering (HRS) was performed with a highly sensitive setup for simultaneous discrimination between multi-photon fluorescence and the molecular first hyperpolarizability.