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

Title: Two-dimensional metal-organic framework constructed from 4,4'-bipydine and 1,2,4-benzenetricarboxylate: Synthesis, structure and magnetic properties

Abstract

Two new copper coordination polymers generated from mixed organic ligands 4,4'-bipydine and 1,2,4-benzenetricarboxylate [Cu{sub 3}(1,2,4-BTC){sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}] 1 and [Cu(1,2,4-HBTC)(4,4'-bipy)] 2 (1,2,4-BTC=1,2,4-benzenetricarboxylate) have been prepared hydrothermally and characterized by single crystal X-ray diffraction. Compound 1 crystallizes in the noncentrosymmetric space group Fdd2, with a=19.004(3)A, b=26.711(4)A, c=11.0770(15)A, V=5622.8(14)A{sup 3}, and Z=8. Its structure contains two different one-dimensional (1-D) chains for the Cu ions, namely [Cu{sub 2}(1,2,4-BTC){sub 2}]{sub n}{sup 2n-} and [Cu(4,4{sup '}-bipy)]{sub n}{sup 2n+}; the carboxylate of 1,2,4-BTC ligands links the two different 1-D chains into an interesting steplike neutral framework. Compound 2 crystallizes in the monoclinic space group P2{sub 1}/n, with a=9.9806(8), b=16.5512(16), c=11.3109(7)A, {beta}=99.375(5){sup o}, V=1843.5(3)A{sup 3}, Z=4. Its structure contains novel paddle-wheel clusters Cu{sub 2}(CO{sub 2}){sub 4}(4,4'-bipy){sub 2} as SBUs which are further linked by monoprotonated 1,2,4-BTC ligands into a 2-D neutral framework. The magnetic behaviors of both compounds have been studied.

Authors:
 [1];  [1];  [1];  [1];  [2]
  1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China)
  2. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China). E-mail: shfeng@mail.jlu.edu.cn
Publication Date:
OSTI Identifier:
20784770
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 178; Journal Issue: 11; Other Information: DOI: 10.1016/j.jssc.2005.08.014; PII: S0022-4596(05)00378-6; 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; COPPER COMPLEXES; COPPER IONS; HYDROTHERMAL SYNTHESIS; LIGANDS; MAGNETIC PROPERTIES; MONOCLINIC LATTICES; MONOCRYSTALS; ORTHORHOMBIC LATTICES; SPACE GROUPS; X-RAY DIFFRACTION

Citation Formats

Wang Lei, Yang Ming, Shi Zhan, Chen Yan, and Feng Shouhua. Two-dimensional metal-organic framework constructed from 4,4'-bipydine and 1,2,4-benzenetricarboxylate: Synthesis, structure and magnetic properties. United States: N. p., 2005. Web. doi:10.1016/j.jssc.2005.08.014.
Wang Lei, Yang Ming, Shi Zhan, Chen Yan, & Feng Shouhua. Two-dimensional metal-organic framework constructed from 4,4'-bipydine and 1,2,4-benzenetricarboxylate: Synthesis, structure and magnetic properties. United States. doi:10.1016/j.jssc.2005.08.014.
Wang Lei, Yang Ming, Shi Zhan, Chen Yan, and Feng Shouhua. Tue . "Two-dimensional metal-organic framework constructed from 4,4'-bipydine and 1,2,4-benzenetricarboxylate: Synthesis, structure and magnetic properties". United States. doi:10.1016/j.jssc.2005.08.014.
@article{osti_20784770,
title = {Two-dimensional metal-organic framework constructed from 4,4'-bipydine and 1,2,4-benzenetricarboxylate: Synthesis, structure and magnetic properties},
author = {Wang Lei and Yang Ming and Shi Zhan and Chen Yan and Feng Shouhua},
abstractNote = {Two new copper coordination polymers generated from mixed organic ligands 4,4'-bipydine and 1,2,4-benzenetricarboxylate [Cu{sub 3}(1,2,4-BTC){sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}] 1 and [Cu(1,2,4-HBTC)(4,4'-bipy)] 2 (1,2,4-BTC=1,2,4-benzenetricarboxylate) have been prepared hydrothermally and characterized by single crystal X-ray diffraction. Compound 1 crystallizes in the noncentrosymmetric space group Fdd2, with a=19.004(3)A, b=26.711(4)A, c=11.0770(15)A, V=5622.8(14)A{sup 3}, and Z=8. Its structure contains two different one-dimensional (1-D) chains for the Cu ions, namely [Cu{sub 2}(1,2,4-BTC){sub 2}]{sub n}{sup 2n-} and [Cu(4,4{sup '}-bipy)]{sub n}{sup 2n+}; the carboxylate of 1,2,4-BTC ligands links the two different 1-D chains into an interesting steplike neutral framework. Compound 2 crystallizes in the monoclinic space group P2{sub 1}/n, with a=9.9806(8), b=16.5512(16), c=11.3109(7)A, {beta}=99.375(5){sup o}, V=1843.5(3)A{sup 3}, Z=4. Its structure contains novel paddle-wheel clusters Cu{sub 2}(CO{sub 2}){sub 4}(4,4'-bipy){sub 2} as SBUs which are further linked by monoprotonated 1,2,4-BTC ligands into a 2-D neutral framework. The magnetic behaviors of both compounds have been studied.},
doi = {10.1016/j.jssc.2005.08.014},
journal = {Journal of Solid State Chemistry},
number = 11,
volume = 178,
place = {United States},
year = {Tue Nov 15 00:00:00 EST 2005},
month = {Tue Nov 15 00:00:00 EST 2005}
}
  • A 3-connected dia-f-type metal-organic framework compound {l_brace}[Ag(L){sub 3/2}H{sub 2}PO{sub 4}]{r_brace}{sub n} (1) has been synthesized by self-assembly of 4,4'-H{sub 2}bpz (L=4,4'-H{sub 2}bpz=3,3',5,5'-tetramethyl-4,4'-bipyrazole) and Ag{sub 4}P{sub 2}O{sub 7} under hydrothermal conditions. It crystallizes in the tetragonal space group I4{sub 1}/acd with a=21.406(4) A, b=21.406(4) A, c=36.298(8) A, Z=32. X-ray single-crystal diffraction reveals that 1 has a three-dimensional framework with an unprecedented alternate left- and right-handed helices structure, featuring a non-uniform two-fold interpenetrated (4.14{sup 2}) net. Photoluminescent investigation reveals that the title compound displays interesting emissions in a wide region, which shows that the title compound may be a good potential candidatemore » as a photoelectric material. - Graphical abstract: A 3-connected dia-f-type metal-organic framework compound [Ag(4,4'-bpz){sub 3/2}H{sub 2}PO{sub 4}] shows unprecedented alternating left- and right-handed helices structure, featuring a non-uniform two-fold interpenetrated (4.14{sup 2}) net.« less
  • A three-dimensional porous metal-organic framework (PCN-18) was constructed through interdigitating two-dimensional grid sheets composed of 4,4{prime}-(anthracene-9,10-diyl)dibenzoate and copper paddlewheel secondary building units, and its dynamic features were evidenced by gas sorption isotherms.
  • Carbon dioxide is a greenhouse gas that is a major contributor to global warming. Developing methods that can effectively capture CO{sub 2} is the key to reduce its emission to the atmosphere. Recent research shows that microporous metal organic frameworks (MOFs) are emerging as a promising family of adsorbents that may be promising for use in adsorption based capture and separation of CO{sub 2} from power plant waste gases. In this work we report the synthesis, crystal structure analysis and pore characterization of two microporous MOF structures, [M{sub 2}(hfipbb){sub 2}(ted)] (M=Zn (1), Co (2); H{sub 2}hfipbb=4,4-(hexafluoroisopropylidene)-bis(benzoic acid); ted=triethylenediamine). The CO{submore » 2} and N{sub 2} adsorption experiments and IAST calculations are carried out on [Zn{sub 2}(hfipbb){sub 2}(ted)] under conditions that mimic post-combustion flue gas mixtures emitted from power plants. The results show that the framework interacts with CO{sub 2} strongly, giving rise to relatively high isosteric heats of adsorption (up to 28 kJ/mol), and high adsorption selectivity for CO{sub 2} over N{sub 2}, making it promising for capturing and separating CO{sub 2} from CO{sub 2}/N{sub 2} mixtures. - Graphical abstract: Microporous [Zn{sub 2}(hfipbb){sub 2}(ted)] demonstrates high adsorption selectivity for CO{sub 2} over N{sub 2} under conditions that mimic flue gas mixtures. Highlights: ► Two new porous MOFs were synthesized and characterized by rational design. ► The small pore size leads to greatly enhanced CO{sub 2}–MOF interaction. ► High adsorption selectivity of the Zn–MOF for CO{sub 2} over N{sub 2} is achieved.« less
  • A novel metal-organic framework (MOF) based on a tetranuclear copper cluster and a linear organic ligand formulated as [Cu{sub 4}OCl{sub 6}(DABCO){sub 2}].0.5DABCO.4CH{sub 3}OH (denoted as MFU-5, MFU=Metal-Organic Framework, Ulm University; DABCO=1,4-diazabicyclo[2.2.2]octane), was prepared via solvothermal synthesis. In contrast with common MOF synthesis strategies, MFU-5 is assembled from pre-defined molecular secondary building units, i.e. {l_brace}Cu{sub 4}OCl{sub 6}{r_brace} moieties, which become the nodes of the coordination framework. The title compound was characterized by single crystal X-ray diffraction, variable temperature powder diffraction (VT-XRPD), thermal analysis, as well as IR- and UV/Vis spectroscopy. Crystal data for MFU-5: hexagonal, P6/mcc (no. 192), a=25.645(9), c=17.105(11) A,more » V=9742(8) A{sup 3}, Z=12, 1690 structure factors, R[F{sup 2}>2sigma(F{sup 2})]=0.049. MFU-5 is a 3D metal-organic framework with 1D channels running along the c-axis hosting DABCO and methanol solvent molecules. The framework displays a zeolite-like structure constructed from mso cages, which represents the composite building units in the zeolites SSF, MSO and SZR. Two-fold interpenetration is observed between these building units. TG/DTA-MS and VT-XRPD characterization reveal a stepwise release of methanol and DABCO molecules upon heating, eventually resulting in a structural change into a non-porous material. - Graphical abstract: The metal-organic framework [Cu{sub 4}OCl{sub 6}(DABCO){sub 2}].0.5DABCO.4CH{sub 3}OH (MFU-5) is constructed from a molecular precursor containing {l_brace}Cu{sub 4}OCl{sub 6}{r_brace} secondary building units which become cross-linked into a 3D zeolite-type network with hexagonal symmetry by linear DABCO ligands (DABCO=1,4-diazabicyclo[2.2.2]octane).« less