skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A magnesium-carboxylate framework showing luminescent sensing for CS{sub 2} and nitroaromatic compounds

Abstract

A magnesium metal-organic framework compound, namely [NH{sub 2}(CH{sub 3}){sub 2}][Mg{sub 3}(NDC){sub 2.5}(HCO{sub 2}){sub 2}(DMF){sub 0.75}(H{sub 2}O){sub 0.25}]·1.25DMF·0.75H{sub 2}O (1) (H{sub 2}NDC=1,4-naphthalene dicarboxylic acid, DMF=N,N′-dimethylformamide), has been synthesized in solvothermal conditions and structurally characterized. It features a three-dimensionally anionic framework with aligned channels parallel to the b-axis. Luminescent studies indicated that it showed significant luminescence quenching for carbon disulfide (CS{sub 2}) and nitrobenzene after being activated, at a content of only 3.0 and 0.1 vol% in DMF, respectively. In addition, the activated sample showed sensitive luminescence quenching for 1,3,5-trinitrophenol with a low concentration of 5×10{sup −5} mol/L. - Graphical abstract: Presented is a microporous 3D Mg-MOF, namely, [NH{sub 2}(CH{sub 3}){sub 2}][Mg{sub 3}(NDC){sub 2.5}(HCO{sub 2}){sub 2}(DMF){sub 0.75}(H{sub 2}O){sub 0.25}]·1.25DMF·0.75H{sub 2}O (1) (H{sub 2}NDC=1,4-naphthalene dicarboxylic acid) showing significant luminescence quenching for carbon disulfide and nitrobenzene. - Highlights: • A microporous 3D metal-organic framework based on Mg. • The compound shows significant luminescence quenching for CS{sub 2} and nitrobenzene after activated. • The compound shows sensitive luminescence quenching for 1,3,5-trinitrophenol with a low concentration of 5×10{sup −5} mol/L.

Authors:
;  [1];  [2];  [1];  [1];  [2];  [1]
  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)
  2. (China)
Publication Date:
OSTI Identifier:
22475538
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 223; Other Information: Copyright (c) 2014 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; CARBON SULFIDES; CHEMICAL PREPARATION; CONCENTRATION RATIO; DICARBOXYLIC ACIDS; DISULFIDES; EXPERIMENTAL DATA; FORMAMIDE; LUMINESCENCE; MAGNESIUM COMPOUNDS; NAPHTHALENE; NITROBENZENE; NITROPHENOL; ORGANOMETALLIC COMPOUNDS; PICRIC ACID; POROSITY; QUENCHING

Citation Formats

Wu, Zhao-Feng, Tan, Bin, University of Chinese Academy of Sciences, Beijing 100049, Feng, Mei-Ling, Du, Cheng-Feng, University of Chinese Academy of Sciences, Beijing 100049, and Huang, Xiao-Ying, E-mail: xyhuang@fjirsm.ac.cn. A magnesium-carboxylate framework showing luminescent sensing for CS{sub 2} and nitroaromatic compounds. United States: N. p., 2015. Web. doi:10.1016/J.JSSC.2014.06.018.
Wu, Zhao-Feng, Tan, Bin, University of Chinese Academy of Sciences, Beijing 100049, Feng, Mei-Ling, Du, Cheng-Feng, University of Chinese Academy of Sciences, Beijing 100049, & Huang, Xiao-Ying, E-mail: xyhuang@fjirsm.ac.cn. A magnesium-carboxylate framework showing luminescent sensing for CS{sub 2} and nitroaromatic compounds. United States. doi:10.1016/J.JSSC.2014.06.018.
Wu, Zhao-Feng, Tan, Bin, University of Chinese Academy of Sciences, Beijing 100049, Feng, Mei-Ling, Du, Cheng-Feng, University of Chinese Academy of Sciences, Beijing 100049, and Huang, Xiao-Ying, E-mail: xyhuang@fjirsm.ac.cn. Sun . "A magnesium-carboxylate framework showing luminescent sensing for CS{sub 2} and nitroaromatic compounds". United States. doi:10.1016/J.JSSC.2014.06.018.
@article{osti_22475538,
title = {A magnesium-carboxylate framework showing luminescent sensing for CS{sub 2} and nitroaromatic compounds},
author = {Wu, Zhao-Feng and Tan, Bin and University of Chinese Academy of Sciences, Beijing 100049 and Feng, Mei-Ling and Du, Cheng-Feng and University of Chinese Academy of Sciences, Beijing 100049 and Huang, Xiao-Ying, E-mail: xyhuang@fjirsm.ac.cn},
abstractNote = {A magnesium metal-organic framework compound, namely [NH{sub 2}(CH{sub 3}){sub 2}][Mg{sub 3}(NDC){sub 2.5}(HCO{sub 2}){sub 2}(DMF){sub 0.75}(H{sub 2}O){sub 0.25}]·1.25DMF·0.75H{sub 2}O (1) (H{sub 2}NDC=1,4-naphthalene dicarboxylic acid, DMF=N,N′-dimethylformamide), has been synthesized in solvothermal conditions and structurally characterized. It features a three-dimensionally anionic framework with aligned channels parallel to the b-axis. Luminescent studies indicated that it showed significant luminescence quenching for carbon disulfide (CS{sub 2}) and nitrobenzene after being activated, at a content of only 3.0 and 0.1 vol% in DMF, respectively. In addition, the activated sample showed sensitive luminescence quenching for 1,3,5-trinitrophenol with a low concentration of 5×10{sup −5} mol/L. - Graphical abstract: Presented is a microporous 3D Mg-MOF, namely, [NH{sub 2}(CH{sub 3}){sub 2}][Mg{sub 3}(NDC){sub 2.5}(HCO{sub 2}){sub 2}(DMF){sub 0.75}(H{sub 2}O){sub 0.25}]·1.25DMF·0.75H{sub 2}O (1) (H{sub 2}NDC=1,4-naphthalene dicarboxylic acid) showing significant luminescence quenching for carbon disulfide and nitrobenzene. - Highlights: • A microporous 3D metal-organic framework based on Mg. • The compound shows significant luminescence quenching for CS{sub 2} and nitrobenzene after activated. • The compound shows sensitive luminescence quenching for 1,3,5-trinitrophenol with a low concentration of 5×10{sup −5} mol/L.},
doi = {10.1016/J.JSSC.2014.06.018},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 223,
place = {United States},
year = {Sun Mar 15 00:00:00 EDT 2015},
month = {Sun Mar 15 00:00:00 EDT 2015}
}
  • A 3D metal–organic framework [NH{sub 2}(CH{sub 3}){sub 2}][Cd{sub 6}(L){sub 4}(DMF){sub 6}(HCOO)](DMF = N,N-dimethylformamide) (1) has been synthesized using a tripodal ligand H{sub 3}L (2,4,6-tris[1-(3-carboxylphenoxy)ylmethyl]mesitylene). The obtained complex exhibits a 3D framework containing hexanuclear (Cd{sub 6}) building units formed by two trinuclear (Cd{sub 3}) clusters that are connected via HCOO{sup −} anions. For complex 1, the participation of the fluorescent ligand H{sub 3}L not only gives rise to a strong photoluminescence emission as expected, but more interestingly, that ligand originated characteristic band could be quenched selectively by nitrobenzene with a low detection limit, showing its potential as a highly sensitive andmore » selective sensor for nitrobenzene. Based on an electron transfer quenching mechanism, the fluorescence sensing ability of 1 is also applicable for other electron-deficient nitroaromatic compounds with high selectivity and sensitivity, i.e., 1,4-dinitrobenzene, 1,3-dinitrobenzene, 2,4-dinitrotoluene, and 4-nitrotoluene, suggesting 1 a promising fluorescence sensor for detecting and recognizing the same kind of chemicals.« less
  • Here, a series of cadmium carboxylate compounds in a sulfur-rich environment provided by the tris(2- tert-butylmercaptoimidazolyl)hydroborato ligand, namely, [Tm But]CdO 2CR, has been synthesized via the reactions of the cadmium methyl derivative [Tm But]CdMe with RCO 2H. Such compounds mimic aspects of cadmium-substituted zinc enzymes and also the surface atoms of cadmium chalcogenide crystals, and have therefore been employed to model relevant ligand exchange processes. Significantly, both 1H and 19F NMR spectroscopy demonstrate that the exchange of carboxylate groups between [Tm But]Cd(κ 2-O 2CR) and the carboxylic acid RCO 2H is facile on the NMR time scale, even at lowmore » temperature. Analysis of the rate of exchange as a function of concentration of RCO 2H indicates that reaction occurs via an associative rather than dissociative pathway. In addition to carboxylate compounds, the thiocarboxylate derivative [Tm But]Cd[κ 1-SC(O)Ph] has also been synthesized via the reaction of [Tm But]CdMe with thiobenzoic acid. The molecular structure of [Tm But]Cd[κ 1-SC(O)Ph] has been determined by X-ray diffraction, and an interesting feature is that, in contrast to the carboxylate derivatives [Tm But]Cd(κ 2-O 2CR), the thiocarboxylate ligand binds in a κ 1 manner via only the sulfur atom.« less
  • Here, a series of cadmium carboxylate compounds in a sulfur-rich environment provided by the tris(2- tert-butylmercaptoimidazolyl)hydroborato ligand, namely, [Tm But]CdO 2CR, has been synthesized via the reactions of the cadmium methyl derivative [Tm But]CdMe with RCO 2H. Such compounds mimic aspects of cadmium-substituted zinc enzymes and also the surface atoms of cadmium chalcogenide crystals, and have therefore been employed to model relevant ligand exchange processes. Significantly, both 1H and 19F NMR spectroscopy demonstrate that the exchange of carboxylate groups between [Tm But]Cd(κ 2-O 2CR) and the carboxylic acid RCO 2H is facile on the NMR time scale, even at lowmore » temperature. Analysis of the rate of exchange as a function of concentration of RCO 2H indicates that reaction occurs via an associative rather than dissociative pathway. In addition to carboxylate compounds, the thiocarboxylate derivative [Tm But]Cd[κ 1-SC(O)Ph] has also been synthesized via the reaction of [Tm But]CdMe with thiobenzoic acid. The molecular structure of [Tm But]Cd[κ 1-SC(O)Ph] has been determined by X-ray diffraction, and an interesting feature is that, in contrast to the carboxylate derivatives [Tm But]Cd(κ 2-O 2CR), the thiocarboxylate ligand binds in a κ 1 manner via only the sulfur atom.« less
  • Two new three-dimensional chromium(III) dicarboxylate, MIL-105 or Cr{sup III}(OH).{l_brace}O{sub 2}C-C{sub 6}(CH{sub 3}){sub 4}-CO{sub 2}{r_brace}.nH{sub 2}O, have been obtained under hydrothermal conditions, and their structures solved using X-ray powder diffraction data. Both solids are structural analogs of the known Cr benzenedicarboxylate compound (MIL-53). Both contain trans corner-sharing CrO{sub 4}(OH){sub 2} octahedral chains connected by tetramethylterephthalate di-anions. Each chain is linked by the ligands to four other chains to form a three-dimensional framework with an array of 1D pores channels. The pores of the high temperature form of the solid, MIL-105ht, are empty. However, MIL-105ht re-hydrates at room temperature to finally givemore » MIL-105lt with pores channels filled with free water molecules (lt: low temperature form; ht: high temperature form). The thermal behaviour of the two solids has been investigated using TGA. Crystal data for MIL-105ht: monoclinic space group C2/c with a = 19.653(1) A, b = 9.984(1) A, c = 6.970(1) A, {beta} = 110.67(1){sup o} and Z = 4. Crystal data for MIL-105lt: orthorhombic space group Pnam with a = 17.892(1) A, b = 11.165(1) A, c = 6.916(1) A and Z = 4.« less
  • A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610 {sup o}C). -- Graphical abstract: The staking of {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite uranyl molybdate ribbons in the Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] structure. Display Omitted Highlights: {yields} Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 2} a new compound with bidimensional crystal structure, characterized by infinite uranyl molybdate chains. {yields} Crystal structure similar to these of the compounds containing Na, K, Rb. {yields} Molybdenum atoms surrounded by five oxygen atoms to form an original and strongly distorted MoO{sub 5} environment. {yields} The chains arrangement illustrates the key role of the alkaline ionic radius, in the crystal structure distortion for Cs compound.« less