Syntheses And Characterization Of Noncentrosymmetric Iodometallate Hybrids

Noncentrosymmetric(NCS) materials are of current interest and great importance owing to their potential applications, such as nonlinear second har monic generation(SHG), ferroelectricity, pyroelectricity, piezoelectric, enantioselective sorption, separation, and catalysis. In situ derived two-winged propeller-like N-benzylpyridinium derivatives and N-benzylquinolinium cations were used as potential asymmetric sources and the iodides of d10 cations(Cu+, Ag+) were used as inorganic components to explore the hierarchically directing effect of SDAs(structure-directing agents) on the construction of noncentrosymmetric iodometallates. The structure-directing mechanism of chiral induction and the synergistic relationship between composition-structure modulation and nonlinear optical properties were also investigated, which provides experimental and theoretical basis and novel methods for the development of nonlinear optical materials. Furthermore, the characterization of single-cr ystal X–ray diffraction, IR, UV–vis optical absorption spectra for seven iodoargentate hybrids shows the structural and band gap modulation, as well as reversible ther mochromism based on inter molecular charge transfer.N-Bz-Py+, N-Bz-Me Py+, and N-Bz-Ql+ cations possess unique spatial and electronic configuration and consequent supramolecular aggregates, showing directing effect on the construction of NCS iodometallates. The successful synthesis of chiral iodocuprate and acentric iodoargentate framework directed by N-Bz-Py+ realize chiral infor mation transfer and the structural matching abilities between organic and inorganic components. The chiral, racemic and centrosymmetric iodocuprate framework were respectively directed by N-Bz-2-Me Py+, N-Bz-3-Me Py+ and N-Bz-4-Me Py+, which shows the substituent effect on chiral infor mation transfer and structural modulation. Compared with N-Bz-Py+ directed iodometallates, the construction of centrosymmetric iodocuprate and iodoargentate framework based on N-Bz-Ql+ indicate the influence of cationic size and conjugated group on chiral infor mation transfer.Moreover, the acentricity or chirality of title compounds were characterized by second order nonlinear properties, which shows different responses in iodoargentate and iodocuprate hybrids. The reversible ther mochromic behavior are affected by electron–accepting ability of cations and electron–giving ability of iodometallates. Therefore, The study of component–structure–proper ty relationship contribute to the development and application of new functional materials.