The first metal carboxylatophosphate, NTHU-2, contains inorganic ZnHPO4 layers linked by BDC units (BDC = 1,4-benzene dicarboxylate or terephthalic anion); the three-dimensional anionic framework has large pores with the smallest diameter being 1.36 nm; N2 sorption isotherms reveal both micro- and mesoporosity; the new material is photoluminescent and disassembles in water wherein the discharged organic fragments form mixed crystals.
Water molecules and terephthalic acid, respectively, exist as a self-assembled monolayer of cyclic (H2O)6 clusters and (TA)infinity chiral chains between the zincophosphate sheets (in blue wires); the irremovable template H3tren3+ ions (in purple wires) are dynamic and could translate back and forth on the sheets during the conversion of the supramolecule contained in one another.
Five new zinc phosphates with differently unique 3D framework topologies, (H3dien)[Zn3(HPO4)3(PO4)] (1), (H2dien)1.5[Zn3(HPO4)3(PO4)] (2), (H3dien)[Zn3(H2PO4)(HPO4)(PO4)2] (3), (H3dien)[Zn3(HPO4)3(PO4)]·1.5H2O (4), and (H4tepa)0.5[Zn2.5(HPO4)2(PO4)]·1.5H2O (5), where dien = H2NC2H4NHC2H4NH2 and tepa = H2N(C2H4NH)3C2H4NH2, have been synthesized under mild hydrothermal or solvothermal conditions and characterized by single-crystal X-ray diffraction, thermal analysis, solid-state NMR, UV–vis, or photoluminescence spectroscopy. Both the 7-atom-skeleton-long dien and the 13-atom-skeleton-long tepa have created 16-membered ring (16R) channels as a common feature in structures 1–5. Their inorganic frameworks are built up with tetrahedra of ZnO4, PO4, and HPO4 (plus H2PO4 in 3) and may all be described as constructed from two-dimensional nets and one- or zero-dimensional units as linkers. Compounds 1–4 have the same Zn/P ratio but possess varied amount of nonframework volume. They are the first examples with dien as template in extra-large-channel structures of zincophosphates. In comparison, the framework of 5 contains a higher value in Zn/P and larger nonframework volume than that in the 24R-channel structure of ND-1. The 16R channels in 1 and 2 are one-dimensional while those in 3, 4, and 5 are unprecedentedly two-dimensional. In this paper, the synthesis, thermal property, NMR, reflectance UV–vis absorption, and photoluminescence study of 1–5 are described; framework topologies, structure relationship, the charge and location of templates, and channel characteristic vs nonframework volume are discussed.
Lanthanoids I 2800 Rb2LnGaSi4O12 (Ln: Y, Eu, Gd, Tb): Luminescent Mixed-Anion Double Layer Silicates Containing Chains of Edge-Sharing LnO 7 Pentagonal Bipyramids. -The four new rare earth gallosilicates (V) and (VII) are isotypic and crystallize in the monoclinic space group I2/a with Z = 8 (single crystal XRD). They are the first examples of rare earth gallosilicates that contain individually occupied tetrahedral Ga 3+ and Si 4+ sites. Characteristic building units of the structure are unbranched achter single silicate chains, infinite chains of edge-sharing LnO 7 pentagonal bipyramids, and the unprecedented mixed-anion double layers of composition [GaSi4O12]. The photoluminescence properties of (Vb) and (VII) are studied. The Y 3+ ion in (Va) can be partially replaced by Eu 3+ and Tb 3+ to produce luminescent materials.
In recent years, materials for ARVR have been actively developed, and high Refractive Index (R.I.) materials are required to achieve high performance and a wide field of view. In addition, AR display is a fine display, therefore the display is needed the materials that can be embedded in fine structures. Since AR has a fine structure, it is formed by nanoimprint (NIL) or gap fill processes. In short, materials with a high R.I., high transparency, and NIL and gap filling properties are required for AR waveguide. High R.I. formulation with high fluidity and low volatility are required for NIL and gap fill process, however, in the case of conventional organic materials, there is the trade-off to obtain high fluidity with low volatility. We designed from the molecular structure and realized to solve the trade-off parameters. With that organic material technology and our unique formulation technology, we have realized products that can perform NIL and gap fill even if it contains a large amount of inorganic nano-filler. In addition, by using organic materials for organic EL, it is possible to obtain effective characteristics such as solvent-free materials with high light extraction efficiency. Products using this technology are expected to be applied to AR and OLED.
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