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Title: Synthesis and properties of pyrazine-pillared Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7} and AgReO{sub 4} layered phases

Abstract

The new pyrazine-pillared solids, AgReO{sub 4}(C{sub 4}H{sub 4}N{sub 2}) (I) and Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7}(C{sub 4}H{sub 4}N{sub 2}){sub 3} (C{sub 4}H{sub 4}N{sub 2}=pyrazine, pyz) (II), were synthesized by hydrothermal methods at 150 deg. C and characterized using single crystal X-ray diffraction (I-P2{sub 1} /c, No. 14, Z=4, a=7.2238(6) A, b=7.4940(7) A, c=15.451(1) A, {beta}=92.296(4){sup o}; II-P2/n, No. 13, Z=2, a=7.6465(9) A, b=7.1888(5) A, c=19.142(2) A, {beta}=100.284(8){sup o}), thermogravimetric analysis, UV-Vis diffuse reflectance, and photoluminescence measurements. Individual Ag(pyz) chains in I are bonded to three perrhenate ReO{sub 4} {sup -} tetrahedra per layer, while each layer in II contains sets of three edge-shared Ag(pyz) chains ({pi}-{pi} stacked) that are edge-shared to four Mo{sub 2}O{sub 4}F{sub 7} {sup 3-} dimers. A relatively small interlayer spacing results from the short length of the pyrazine pillars, and which can be removed at just slightly above their preparation temperature, at >150-175 deg. C, to produce crystalline AgReO{sub 4} for I, and Ag{sub 2}MoO{sub 4} and an unidentified product for II. Both pillared solids exhibit strong orange-yellow photoemission, at 575 nm for I and 560 nm for II, arising from electronic excitations across (charge transfer) band gaps of 2.91 and 2.76 eV in each, respectively.more » Their structures and properties are analyzed with respect to parent 'organic free' silver perrhenate and molybdate solids which manifest similar photoemissions, as well as to the calculated electronic band structures. -- Graphical abstract: Two new pyrazine-pillared hybrid solids have been synthesized under hydrothermal conditions, Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7}(pyz){sub 3} (shown) and AgReO{sub 4}(pyz). These solids are novel examples of layered structures containing pillaring Ag(pyz) chains and also the unique Mo{sub 2}O{sub 4}F{sub 7} {sup 3-} dimer in the former. Both exhibit orange-yellow photoluminescence, and the pyrazine pillars can be removed at slightly above the synthesis temperatures to give corresponding crystalline metal-oxide phases.« less

Authors:
 [1];  [1];  [1];  [2]
  1. Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204 (United States)
  2. Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204 (United States). E-mail: Paul_Maggard@ncsu.edu
Publication Date:
OSTI Identifier:
20784852
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2005.10.037; PII: S0022-4596(05)00490-1; Copyright (c) 2005 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; EV RANGE 01-10; FLUORIDES; LAYERS; MOLYBDATES; MONOCLINIC LATTICES; OPTICAL PROPERTIES; PHOTOEMISSION; PHOTOLUMINESCENCE; RHENIUM COMPOUNDS; SILVER COMPOUNDS; SYNTHESIS; THERMAL GRAVIMETRIC ANALYSIS; X-RAY DIFFRACTION

Citation Formats

Lin Haisheng, Yan Bangbo, Boyle, Paul D., and Maggard, Paul A. Synthesis and properties of pyrazine-pillared Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7} and AgReO{sub 4} layered phases. United States: N. p., 2006. Web.
Lin Haisheng, Yan Bangbo, Boyle, Paul D., & Maggard, Paul A. Synthesis and properties of pyrazine-pillared Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7} and AgReO{sub 4} layered phases. United States.
Lin Haisheng, Yan Bangbo, Boyle, Paul D., and Maggard, Paul A. Sun . "Synthesis and properties of pyrazine-pillared Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7} and AgReO{sub 4} layered phases". United States. doi:.
@article{osti_20784852,
title = {Synthesis and properties of pyrazine-pillared Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7} and AgReO{sub 4} layered phases},
author = {Lin Haisheng and Yan Bangbo and Boyle, Paul D. and Maggard, Paul A.},
abstractNote = {The new pyrazine-pillared solids, AgReO{sub 4}(C{sub 4}H{sub 4}N{sub 2}) (I) and Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7}(C{sub 4}H{sub 4}N{sub 2}){sub 3} (C{sub 4}H{sub 4}N{sub 2}=pyrazine, pyz) (II), were synthesized by hydrothermal methods at 150 deg. C and characterized using single crystal X-ray diffraction (I-P2{sub 1} /c, No. 14, Z=4, a=7.2238(6) A, b=7.4940(7) A, c=15.451(1) A, {beta}=92.296(4){sup o}; II-P2/n, No. 13, Z=2, a=7.6465(9) A, b=7.1888(5) A, c=19.142(2) A, {beta}=100.284(8){sup o}), thermogravimetric analysis, UV-Vis diffuse reflectance, and photoluminescence measurements. Individual Ag(pyz) chains in I are bonded to three perrhenate ReO{sub 4} {sup -} tetrahedra per layer, while each layer in II contains sets of three edge-shared Ag(pyz) chains ({pi}-{pi} stacked) that are edge-shared to four Mo{sub 2}O{sub 4}F{sub 7} {sup 3-} dimers. A relatively small interlayer spacing results from the short length of the pyrazine pillars, and which can be removed at just slightly above their preparation temperature, at >150-175 deg. C, to produce crystalline AgReO{sub 4} for I, and Ag{sub 2}MoO{sub 4} and an unidentified product for II. Both pillared solids exhibit strong orange-yellow photoemission, at 575 nm for I and 560 nm for II, arising from electronic excitations across (charge transfer) band gaps of 2.91 and 2.76 eV in each, respectively. Their structures and properties are analyzed with respect to parent 'organic free' silver perrhenate and molybdate solids which manifest similar photoemissions, as well as to the calculated electronic band structures. -- Graphical abstract: Two new pyrazine-pillared hybrid solids have been synthesized under hydrothermal conditions, Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7}(pyz){sub 3} (shown) and AgReO{sub 4}(pyz). These solids are novel examples of layered structures containing pillaring Ag(pyz) chains and also the unique Mo{sub 2}O{sub 4}F{sub 7} {sup 3-} dimer in the former. Both exhibit orange-yellow photoluminescence, and the pyrazine pillars can be removed at slightly above the synthesis temperatures to give corresponding crystalline metal-oxide phases.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 179,
place = {United States},
year = {Sun Jan 15 00:00:00 EST 2006},
month = {Sun Jan 15 00:00:00 EST 2006}
}