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Title: Crystal structures and spectroscopic properties of a new zinc phosphite cluster and an unexpected chainlike zinc phosphate obtained by hydrothermal reactions

Abstract

A new zinc phosphite cluster, Zn{sub 2}(4,4'-dmbpy){sub 2}(H{sub 2}PO{sub 3}){sub 4}1, and a new chainlike zinc phosphate, Zn{sub 2}(5,5'-dmbpy){sub 2}(HPO{sub 4})(H{sub 2}PO{sub 4}){sub 2}2, have been synthesized under hydrothermal conditions (4,4'-dmbpy=4,4'-dimethyl-2,2'-dipyridy, 5,5'-dmbpy=5,5'-dimethyl-2,2'-dipyridy). Compound 1 is a molecular zinc phosphite constructed from ZnO{sub 3}N{sub 2} trigonal bipyramids, H{sub 2}PO{sub 3} pseudo-pyramids and 4,4'-dmbpy ligands. Compound 2 possesses a 1D chainlike framework constructed from ZnO{sub 3}N{sub 2} trigonal bipyramids, HPO{sub 4} tetrahedra, H{sub 2}PO{sub 4} tetrahedra and 5,5'-dmbpy ligands. Both compounds 1 and 2 exhibit intensive photoluminescence originated from the intraligand {pi}-{pi}* transitions. Crystal data: 1, monoclinic, P2{sub 1}/n, a=8.0310(7)A, b=20.2301(5)A, c=10.8424(2)A, {beta}=110.857(3){sup o}, V=1646.11(15)A{sup 3}, Z=2, R1=0.0297, wR{sub 1}=0.0801; 2, triclinic, P-1, a=11.6875(8)A, b=12.3498(7)A, c=13.1759(8)A, {alpha}=64.995(9){sup o}, {beta}=65.952(9){sup o}, {gamma}=65.296(8){sup o}, V=1502.99(16)A{sup 3}, Z=2, R{sub 1}=0.0418, wR{sub 1}=0.1010.

Authors:
 [1];  [1];  [1];  [2]
  1. Department of Chemical System Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
  2. Department of Chemical System Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan), E-mail: okubo@chemsys.t.u-tokyo.ac.jp
Publication Date:
OSTI Identifier:
21015737
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2006.12.025; PII: S0022-4596(07)00006-0; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; HYDROTHERMAL SYNTHESIS; LIGANDS; MONOCLINIC LATTICES; PHOTOLUMINESCENCE; ZINC COMPLEXES; ZINC PHOSPHATES

Citation Formats

Lin Zhien, Fan Wei, Gu Jinlou, and Okubo, Tatsuya. Crystal structures and spectroscopic properties of a new zinc phosphite cluster and an unexpected chainlike zinc phosphate obtained by hydrothermal reactions. United States: N. p., 2007. Web.
Lin Zhien, Fan Wei, Gu Jinlou, & Okubo, Tatsuya. Crystal structures and spectroscopic properties of a new zinc phosphite cluster and an unexpected chainlike zinc phosphate obtained by hydrothermal reactions. United States.
Lin Zhien, Fan Wei, Gu Jinlou, and Okubo, Tatsuya. Thu . "Crystal structures and spectroscopic properties of a new zinc phosphite cluster and an unexpected chainlike zinc phosphate obtained by hydrothermal reactions". United States. doi:.
@article{osti_21015737,
title = {Crystal structures and spectroscopic properties of a new zinc phosphite cluster and an unexpected chainlike zinc phosphate obtained by hydrothermal reactions},
author = {Lin Zhien and Fan Wei and Gu Jinlou and Okubo, Tatsuya},
abstractNote = {A new zinc phosphite cluster, Zn{sub 2}(4,4'-dmbpy){sub 2}(H{sub 2}PO{sub 3}){sub 4}1, and a new chainlike zinc phosphate, Zn{sub 2}(5,5'-dmbpy){sub 2}(HPO{sub 4})(H{sub 2}PO{sub 4}){sub 2}2, have been synthesized under hydrothermal conditions (4,4'-dmbpy=4,4'-dimethyl-2,2'-dipyridy, 5,5'-dmbpy=5,5'-dimethyl-2,2'-dipyridy). Compound 1 is a molecular zinc phosphite constructed from ZnO{sub 3}N{sub 2} trigonal bipyramids, H{sub 2}PO{sub 3} pseudo-pyramids and 4,4'-dmbpy ligands. Compound 2 possesses a 1D chainlike framework constructed from ZnO{sub 3}N{sub 2} trigonal bipyramids, HPO{sub 4} tetrahedra, H{sub 2}PO{sub 4} tetrahedra and 5,5'-dmbpy ligands. Both compounds 1 and 2 exhibit intensive photoluminescence originated from the intraligand {pi}-{pi}* transitions. Crystal data: 1, monoclinic, P2{sub 1}/n, a=8.0310(7)A, b=20.2301(5)A, c=10.8424(2)A, {beta}=110.857(3){sup o}, V=1646.11(15)A{sup 3}, Z=2, R1=0.0297, wR{sub 1}=0.0801; 2, triclinic, P-1, a=11.6875(8)A, b=12.3498(7)A, c=13.1759(8)A, {alpha}=64.995(9){sup o}, {beta}=65.952(9){sup o}, {gamma}=65.296(8){sup o}, V=1502.99(16)A{sup 3}, Z=2, R{sub 1}=0.0418, wR{sub 1}=0.1010.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 180,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}
  • The organically templated (C{sub 6}H{sub 16}N{sub 2}){sub 0.5}[M(HPO{sub 3})F] [M(II)=Fe (1) and Co (2)] compounds have been synthesized by using mild hydrothermal conditions under autogeneous pressure. The crystal structures have been determined from X-ray single-crystal diffraction data. The compounds are isostructural and crystallize in the C2/c monoclinic space group. The unit-cell parameters are a=5.607(1), b=21.276(4), c=11.652(1)A, {beta}=93.74(1) deg. for the iron phase and a=5.5822(7), b=21.325(3), c=11.4910(1)A, {beta}=93.464(9){sup o} for the cobalt compound with Z=4. The crystal structure of these compounds consists of [M(HPO{sub 3})F]{sup -} anionic sheets. The layers are constructed from chains which contain [M{sub 2}O{sub 6}F{sub 3}] dimericmore » units linked by fluoride ions. The trans-1,4-diaminocyclohexane cations are placed in the interlayer space. The IR and Raman spectra show the bands corresponding to the phosphite oxoanion and organic dication. The Dq and Racah (B and C) parameters have been calculated from the diffuse reflectance spectra in the visible region. Dq parameter is 790cm{sup -1} for compound (1). For phase (2) the Dq value is 725cm{sup -1} and B and C are 930 and 4100cm{sup -1}, respectively. The thermal evolution of the molar magnetic susceptibilities of these compounds show maxima at 20.0 and 6.0K for the iron(II) and cobalt(II) phases, respectively. These results indicate the existence of antiferromagnetic interactions in both compounds.« less
  • A new manganese(II) phosphate templated by ethylenediamine, (C{sub 2}H{sub 10}N{sub 2})[Mn{sub 2}(HPO{sub 4}){sub 3}(H{sub 2}O)], has been prepared by hydrothermal synthesis and characterized by single-crystal diffraction data and spectroscopic and magnetic techniques. The compound crystallizes in the monoclinic space group P2{sub 1}/n with a = 21.961(7), b = 9.345(1), c = 6.639(2) {angstrom}; {beta} = 91.06(2){degree}; V = 1362.3(6) {angstrom}{sup 3}; and Z = 4. The structure consists of anionic sheets of formula [Mn{sub 2}(HPO{sub 4}){sub 3}]{sup 2-}, being the charge compensated by ethylendiammonium cations. The sheets are constructed by edge-sharing MnO{sub 6} octahedra, MnO{sub 5} trigonal bipyramids, and hydrogenmore » phosphate tetrahedra. Within a layer, the edge-sharing octahedra and the trigonal bipyramids are linked in an alternating way, forming zigzag chains along the [001] direction. The ethylenediammonium cations and the water molecules are located in the interlayer space. The compound has been characterized by IR spectroscopy. A study of the compound by luminescence and diffuse reflectance spectroscopies is carried out. The Dq and Racah parameters have been calculated for Mn(II) ions in octahedral sites. The EST spectra at different temperatures of the compound show isotropic signals, with a g value that remains unchanged with variation in temperature. The intensity and the line width of the ESR signals increase continuously from room temperature to 4.2 K. Magnetic measurements from room temperature to 1.8 K indicate the presence of antiferromagnetic interactions. A value of J/k = {minus}0.75 K for the exchange parameter has been calculated by fitting the experimental magnetic data to a triangular lattice antiferromagnet of S = 5/2 spins.« less
  • A series of zirconium phosphate fluorides were synthesized and structurally characterized using different amines as templates. The compounds have the general formulas [amH{sub n}]{sub 1/n}[Zr{sub 2}(HPO{sub 4})(PO{sub 4}){sub 2}F]{center_dot}H{sub 2}O (1, am = ethylenediamine, n = 2; 2. am = N-methylethylenediamine, n = 2; 3, am = 1,3-diaminopropane, n = 2; 4, am = diethylenetriamine, n = 3) and [amH{sub 2}]{sub 0.5}[Zr{sub 2}(HPO{sub 4}){sub 2}(PO{sub 4})F{sub 2}]{center_dot}0.5H{sub 2}O (5, am = N,N,N{prime},N{prime}-tetramethylethylenediamine). In the structures of 2--4 with a Zr:F ratio of 2:1, there exists a three-dimensional arrangement of zirconium octahedra (one ZrO{sub 6} and one ZrO{sub 5}F) and phosphatemore » tetrahedra (two PO{sub 4} and one HPO{sub 4}) connected via common oxygen atoms, whereas fluorine atoms and OH groups are terminal. These compounds crystallize in the ZrPO-1 structure type, which contains channels along the b axis formed by eight-membered rings of alternating PO{sub 4} tetrahedra and ZrO{sub 6} or ZrO{sub 5}F octahedra, respectively. The protonated disordered templates occupy the channels. Half the water molecules are situated in the positions alternatively left free by the disordered templates and the other half are bonded via hydrogen bridges to the terminal OH groups of the HPO{sub 4} tetrahedra. In contrast, the structure of 5 reveals a Zr:F ratio of 1:1, consequently forming a layer structure. The layers formed by ZrO{sub 5}F octahedra and PO{sub 4} or HPO{sub 4} tetrahedra, respectively, are linked by hydrogen bridges of type O{single_bond}H{hor_ellipsis}F and by weak H bonds over the protonated template. The similarities in connectivity pattern between Zr octahedra and P tetrahedra in all known zirconium phosphate fluorides and some zirconium phosphates are discussed.« less
  • Five new coordination polymers, [Zn{sub 2}(ctpy){sub 2}Cl{sub 2}]{sub n} (1), [Zn{sub 2}(ctpy){sub 2}(ox)(H{sub 2}O){sub 2}]{sub n} (2), [Zn{sub 2}(ctpy)(3-btc)(H{sub 2}O)]{sub n}{center_dot}0.5nH{sub 2}O (3), [Cd(ctpy){sub 2}(H{sub 2}O)]{sub n} (4), [Cd{sub 4}(ctpy){sub 2}(2-btc){sub 2}(H{sub 2}O){sub 2}]{sub n}{center_dot}2nH{sub 2}O (5), (Hctpy=3,2 Prime :6 Prime ,3 Prime Prime -terpyridine-4 Prime -carboxylic acid, H{sub 2}ox=oxalic acid, H{sub 3}(3-btc)=1,3,5-benzenetricarboxylic acid, H{sub 3}(2-btc)=1,2,4-benzenetricarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Compounds 1-2 are a one-dimensional chain with weak interactions to form 3D supramolecular structures. Compound 3 is a 4-nodal 3D topology framework comprised of binuclear zincmore » units and (ctpy){sup -} anions. Compound 4 shows two dimensional net. Compound 5 is a (4,5,6)-connected framework with {l_brace}4{sup 4}{center_dot}6{sup 2}{r_brace}{l_brace}4{sup 6}{center_dot}6{sup 4}{r_brace}{sub 2}{l_brace}4{sup 9}{center_dot}6{sup 6}{r_brace} topology. In addition, the thermal stabilities and photoluminescence properties of 1-5 were also studied in the solid state. - Graphical abstract: Five new Zn/Cd compounds with 3,2 Prime :6 Prime ,3 Prime Prime -terpyridine-4 Prime -carboxylic acid were prepared. The photoluminescence and thermal stabilities properties of 1-5 were investigated in the solid state. Highlights: Black-Right-Pointing-Pointer Five new zinc/cadmium metal-organic frameworks have been hydrothermal synthesized. Black-Right-Pointing-Pointer The structural variation is attributed to the diverse metal ions and auxiliary ligand. Black-Right-Pointing-Pointer Compounds 1-5 exhibit 1D ring chain, 2D layer and 3D open-framework, respectively. Black-Right-Pointing-Pointer These compounds exhibit strong solid state luminescence emission at room temperature.« less
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