Cd2 Nb2 Te4 O15 : A Novel Pseudo-Aurivillius-Type Tellurite with Unprecedented Nonlinear Optical Properties and Excellent Stability.

Oxides are emerging candidates for mid-infrared (mid-IR) nonlinear optical (NLO) materials. However, their intrinsically weak second harmonic generation (SHG) effects hinder their further development. A major design challenge is to increase the nonlinear coefficient while maintaining the broad mid-IR transmission and high laser-induced damage threshold (LIDT) of the oxides. In this study, it is reported on a polar NLO tellurite, Cd2 Nb2 Te4 O15 (CNTO), featuring a pseudo-Aurivillius-type perovskite layered structure composed of three types of NLO active groups, including CdO6 octahedra, NbO6 octahedra, and TeO4 seesaws. The uniform orientation of the distorted units induces a giant SHG response that is ≈31 times larger than that of KH2 PO4 , the largest value among all reported metal tellurites. Additionally, CNTO exhibits a large band gap (3.75 eV), a wide optical transparency window (0.33-14.5 µm), superior birefringence (0.12@ 546 nm), high LIDT (23 × AgGaS2 ), and strong acid and alkali resistance, indicating its potential as a promising mid-IR NLO material.

Plasma-catalysed reaction Mn+ + L-H → MOFs: facile and tunable construction of metal-organic frameworks in dielectric barrier discharge.

A fast (down to 1 min), power-saving (watt) and green strategy was proposed for preparing diverse and fine-tuned metal-organic frameworks (MOFs) and MOFs-based composites in either DMF or ethanol, catalyzed by liquid-phase plasma generated via dielectric barrier discharge (DBD).

A 3D aluminoborate open framework interpenetrated by 2D zinc-amine coordination-polymer networks in its 11-ring channels.

A new inorganic-organic hybrid solid, [Zn(dap)2 ][AlB5 O10 ], combining the structural features of 3D open-framework inorganic solids and 2D metal-organic coordination polymers has been synthesized under solvothermal conditions. The compound displays extensive luminescence and moderate second-harmonic-generation efficiency.

A pillared-layered zincoborate with an anionic network containing unprecedented zinc oxide chains.

A semiconducting zincoborate with a pillared-layered structure, has been prepared under solvothermal conditions, showing the first example of an inorganic-organic hybrid zincoborate with an anionic network based on the interesting zinc oxide chains linked by boron atoms and B3O7H2 clusters, which are further pillared by diamine molecules to form the 3-D framework.

Germanates of 1D chains, 2D layers, and 3D frameworks built from Ge-O clusters by using metal-complex templates: host-guest symmetry and chirality transfer.

The self-assembly of Ge-O polyhedra by metal-complex templates leads to initial examples of open germanate structures under mild solvothermal conditions. These materials are constructed from Ge-O cluster building blocks (Ge7X19 (X = O, OH, or F) or Ni@Ge14O24(OH)3) and span the full range of dimensionalities from 1D chains of Ge7O13(OH)2F3 x Cl x 2 [Ni(dien)2] (FJ-6) to 2D layers of Ge7O14F3 x 0.5 [In(dien)2] x 0.5 H3dien x 2 H2O (1) and 3D frameworks of Ni@ Ge14O24(OH)3 x 2 [Ni(L)3] (FJ-1 a/FJ-1 b) (dien = diethylenetriamine, L = ethylenediamine (en) or 1,2-diaminopropane (enMe)). The Ge7X19 cluster in FJ-6 and 1 is formed by condensation of four GeX4 tetrahedra, two GeX5 trigonal bipyramids, and one GeX6 octahedron with a mu3-O atom at the center of the cluster, whereas the Ni@ Ge14O24(OH)3 cluster in FJ-1 a/FJ-1 b is formed by condensation of nine peripheral GeO4 tetrahedra and five interior GeO3Ni units with one mu5-Ni atom at the center of the cluster. FJ-6 is characterized by a pair of racemic Ge7O14(OH)2F3 cluster chains and represents only one example of 1D germanates; 1 exhibits unique germanate layers with uniform 10-membered-ring apertures encapsulating an unknown indium complex, and the framework structure of FJ-1 a/FJ-1 b with large 24-membered-ring channels is the first example of porous materials that contain metal-metal bonds (Ge2+-Ni+). These initial examples of germanates from metal-complex templates provide a useful model system for understanding the mechanisms of host-guest interactions, which may further facilitate the design and development of new porous materials "on demand". It is shown that the symmetry and configuration of the guest metal complex can be imprinted onto the host inorganic framework through hydrogen bonding between host and guest.

Ga(2,2'-bipy)(HPO(4))(H(2)PO(4)): first layered inorganic-organic hybrid gallium phosphate with a neutral framework.

A novel gallium phosphate, Ga(2,2'-bipy)(HPO(4))(H(2)PO(4)) (denoted FJ-12; FJ = Fujian Institute of Research on the Structure of Matter), which is the first example of layered inorganic-organic hybrid gallium phosphate with neutral framework, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. This compound crystallizes in the monoclinic system, space group P2(1)/c (No. 14), with a = 10.9443(9), b = 15.8253(13), and c = 8.4201(7) A, beta = 108.898(2) degrees, V = 1379.7(2) A(3), and Z = 4. The structure consists of HPO(4) and H(2)PO(4) tetrahedra and unusual GaO(4)N(2) octahedra which are linked through their vertexes forming an undulated sheetlike structure with 4.12-net. The adjacent layers are stably packed together and exhibit interesting 3-D supramolecular arrays pi-pi interactions of the 2,2'-bipy groups.

Synthesis and Structure of KBGe2O6: the first chiral zeotype borogermanate with 7-ring channels.

Among the known zeolite topologies, odd rings are rare with the exception of 5-ring. We report here the hydrothermal synthesis and structural characterization of a novel compound, KBGe(2)O(6), the first germanate-based zeotype material with 7-ring channels. It crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), a = 4.8037(3) A, b = 10.2063(7) A, c = 10.7402(10) A, V = 526.57(5) A(3), Z = 3. The framework topology of this compound is previous unknown with the vertex symbol 4.6.4.6.6.7(2)(vertex1), 4.6.4.6.6.7(2)(vertex2), and 6.6.6.6.6(2) x 7(2)(vertex3). It is worth noting that the structure of the compound is chiral containing helices condensed from GeO(4) tetrahedra, which arrange around 2(1) screw axes. Furthermore, the K(+) ions within the channels are mobile and can be partially ion-exchanged with Na(+) at room temperature.