Synthesis and structural characterization of a new open-framework zinc terephthalate Zn{sub 3}(OH){sub 2}(bdc){sub 2}.2DEF, with infinite Zn-({mu}{sub 3}-OH)-Zn chains
- Institut Lavoisier (UMR CNRS 8637), Universite de Versailles St Quentin en Yvelines, 45, Avenue des Etats Unis, FR-78035 Versailles Cedex (France)
A new zinc carboxylate Zn{sub 3}(OH){sub 2}(bdc){sub 2}.2DEF was synthesized under mild hydrothermal conditions (100{sup o}C, 40h) in the presence of 1,4-benzenedicarboxylic (bdc) acid, in N,N'-diethylformamide (DEF) solvent. Its structure, characterized by means of single-crystal XRD analysis, consists of connection of ZnO{sub 2}(OH){sub 2} tetrahedra corner-sharing with ZnO{sub 4}(OH){sub 2} octahedra. Two adjacent ZnO{sub 2}(OH){sub 2} tetrahedra have a common edge corresponding to hydroxy group, which is also linked to the octahedrally coordinated zinc atoms with a {mu}{sub 3} configuration. This resulting connection mode generates infinite chains running along the c-axis, and connected to each other via the bdc ligand. Three-dimensional framework is therefore formed with channels running along the c-axis, parallel to the infinite Zn-OH-Zn chains. Within the tunnels are trapped the DEF species, which interacts via hydrogen-bond to the {mu}{sub 3}-hydroxy of the zinc chains with the terminal oxygen atom of the formamide function. Analysis by solid state NMR ({sup 1}H and {sup 13}C) has confirmed both the presence of occluded solvent molecules within the pores and the incorporation of carboxylate moieties into the framework. The structure of Zn{sub 3}(OH){sub 2}(bdc){sub 2}.2DEF is closely related to those of MOF-69 series, constructed with longer organic linkers (4,4'-biphenyldicarboxylate and 2,6-naphthalenedicarboxylate). The structure is observed to loose crystallinity upon heating and removal of the occluded DEF moieties. Crystal data for [Zn{sub 9}(OH){sub 6}(O{sub 2}C-C{sub 6}H{sub 4}-CO{sub 2}){sub 6}].6[(CH{sub 3}-CH{sub 2}){sub 2}NCHO]: a=17.7374(3)A, b=15.2605(2)A, c=18.2635(2)A, {beta}=113.071(1){sup o}, V=4548.2(1)A{sup 3}, P2{sub 1}/n (no. 14), Z=1, R{sub 1}=0.0510, wR{sub 2}=0.1302 for 11877 reflections I>2{sigma}(I)
- OSTI ID:
- 20725815
- Journal Information:
- Journal of Solid State Chemistry, Vol. 178, Issue 3; Other Information: DOI: 10.1016/j.jssc.2004.12.004; PII: S0022-4596(04)00643-7; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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