Synergetic Influence of Alkali-Metal and Lone-Pair Cations on Frameworks of Tellurites

Four new tellurites were hydrothermally synthesized by the adjustment of different alkali-metal ions, and all of the compounds demonstrate 2D layer structures. Rb2Te4O9 center dot 2H(2)O in centrosymmetric space group Pccn features a new [Te4O9](infinity)(2-) anion sheet consisting of rare [Te8O22](12-) groups. RbNaTe8O14(OH)(6).8H(2)O in CS space group P1 exhibits a [Te4O9](infinity)(2-) anion layer by linkage of the TeO3 and TeO4 units. NaPb4Te4O12F located in CS space group P4/n displays an unusual [PbTe03]. neutral layer made up of PbO3 and TeO3 trigonal pyramids. RbK3Te8O18 center dot 5H(2)O lying in noncentrosymmetric (NCS) space group Cc shows a [Te409]oo- anion layer composed of the TeO3 and TeO4 units; its second-harmonic-generation response is about 0.2 times that of KH2PO4; structure analysis and local dipole moment calculation verify that the weak polarization mostly from the [Te4O9](infinity)(2-) layer results from the inverse arrangement of TeO units, and further theoretical calculation confirms that Te0 groups dominate the band gap of RbK3Te8O18-5H(2)O and optical properties. Meanwhile, systematic analyses of a series of metal tellurites reveal that the alkali-metal cations exert a considerable impact on polarization of the crystal structures, which puts forward a feasible idea about the design of new NCS materials.