In-situ carboxylation and synthesis of two novel Sm(III) coordination polymers assembled from 5-hydroxyisophthalate and nitrate, chloride in hydrothermal reaction
- Department of Chemistry, Tongji University, Shanghai 200092 (China)
- Department of Chemistry, College of Science, Shanghai University, Shanghai 200444 (China)
By reactions of 5-hydroxyisophthalic acid (H{sub 2}hisp) with Sm(NO{sub 3}){sub 3}.6H{sub 2}O or SmCl{sub 3}.6H{sub 2}O in the presence of NaOH, two kinds of samarium coordination polymers, [Sm(H{sub 2}hbtc)(ox){sub 0.5}(H{sub 2}O){sub 3}]{sub n}.nH{sub 2}O (1) (H{sub 2}hbtc{sup 2-}=6-hydroxy-1,2,4-benzenetricarboxylate) and [Sm(hisp)(Hhisp)(H{sub 2}O){sub 2}]{sub n}.2nH{sub 2}O (2), have been hydrothermal synthesized and characterized. Single-crystal X-ray analyses reveal that compound 1 features a novel two-dimensional (2D) stair-like structure with oxalate ligands and the new organic ligand (H{sub 2}hbtc{sup 2-}) but without 5-hydroxyisophthalate ligands, while compound 2 gives the expected product and displays a novel layer structure. The oxalate ligands have been formed via the in-situ reductive coupling of CO{sub 2} molecules released from the decomposition of carboxylate ligands with the reduction of NO{sub 3}{sup -} and the new organic ligands have been formed via the in-situ carboxylation under the presence of NO{sub 3}{sup -}. Reported herein are the syntheses of compounds 1 and 2, crystal structures and possible mechanism information regarding the in-situ carboxylation. - Graphical abstract: Hydrothermal reactions of Sm(NO{sub 3}){sub 3}.6H{sub 2}O or SmCl{sub 3}.6H{sub 2}O with 5-hydroxyisophthalic acid (H{sub 2}hisp) have given rise to two different kinds of Sm(III) coordination polymers. Single-crystal X-ray analyses reveal that compound 1 features a novel 2D stair-like structure with oxalate and a new organic ligand, 6-hydroxy-1,2,4-benzenetricarboxylate, while compound 2 gives the normal product and displays a novel 2D layer structure. Oxalate ligands have been formed via the in-situ reductive coupling of CO{sub 2} molecules released from the decomposition of 5-hydroxyisophthalate ligands with the reduction of NO{sub 3}{sup -} and the new organic ligands have been formed via the in-situ carboxylation under the presence of NO{sub 3}{sup -}.
- OSTI ID:
- 21212087
- Journal Information:
- Journal of Solid State Chemistry, Vol. 181, Issue 11; Other Information: DOI: 10.1016/j.jssc.2008.07.027; PII: S0022-4596(08)00395-2; Copyright (c) 2008 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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