Syntheses, structure determinations, and characterization of a series of new noncentrosymmetric (NCS) materials will be presented. The NCS materials are composed of second-order Jahn Teller (SOJT) distortive cations, i.e., d0 transition metal cations and stereoactive lone pair cations. Powder second-harmonic generation (SHG) properties and the structure-property relationships for the NCS materials are discussed. The SHG efficiency is understood by examining the polarization of the asymmetric polyhedral. The origin and the magnitude of the SHG properties will be elucidated by determining the net direction of the polarizations. In addition, several new coordination polymers with asymmetric coordination environments are introduced. Thermal stabilities, gas adsorption, reversible hydrations, and ligand exchange reactions for the metal-organic materials will be presented.