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.

No abstract

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.

No abstract