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Title: Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

Abstract

Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2{sub 1} helical chains. While the Nd(III) ions are bridged through μ{sub 2}-HIDC{sup 2−} and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2{sub 1} helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2{sub 1} helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature.

Authors:
;  [1];  [2]; ; ;  [1];  [1];  [3]; ; ;  [1]
  1. Technology Promotion Center of Nano Composite Material Preparation and Application, Anhui Provincial Laboratory of Biomimetic Sensor and Detecting Technology, West Anhui University, Lu’an, Anhui 237012 (China)
  2. Shandong Collegial Key Laboratory of Biotechnology and Utilization of Biological Resources, College of Life Science, Dezhou University, Dezhou 253023, P.R.China (China)
  3. College of Chemistry & Chemical Engineering, Shaanxi University of Science & Techology, Xi’an, Shaanxi, 710021 (China)
Publication Date:
OSTI Identifier:
22475597
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 225; Other Information: Copyright (c) 2015 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; AMIDES; COORDINATION NUMBER; CRYSTALS; FLUORESCENCE; FORMATES; LAYERS; OXALATES; OXALIC ACID; PHOSPHORESCENCE; POLYMERS; RARE EARTH COMPLEXES; RARE EARTHS; SOLIDS; SOLVENTS; TEMPERATURE RANGE 0273-0400 K; ULTRAVIOLET RADIATION

Citation Formats

Jin, Jun-Cheng, Tong, Wen-Quan, Fu, Ai-Yun, Xie, Cheng-Gen, Chang, Wen-Gui, Wu, Ju, Xu, Guang-Nian, E-mail: xuguangnian@126.com, Zhang, Ya-Nan, Li, Jun, Li, Yong, and Yang, Peng-Qi. Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide. United States: N. p., 2015. Web. doi:10.1016/J.JSSC.2014.12.026.
Jin, Jun-Cheng, Tong, Wen-Quan, Fu, Ai-Yun, Xie, Cheng-Gen, Chang, Wen-Gui, Wu, Ju, Xu, Guang-Nian, E-mail: xuguangnian@126.com, Zhang, Ya-Nan, Li, Jun, Li, Yong, & Yang, Peng-Qi. Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide. United States. doi:10.1016/J.JSSC.2014.12.026.
Jin, Jun-Cheng, Tong, Wen-Quan, Fu, Ai-Yun, Xie, Cheng-Gen, Chang, Wen-Gui, Wu, Ju, Xu, Guang-Nian, E-mail: xuguangnian@126.com, Zhang, Ya-Nan, Li, Jun, Li, Yong, and Yang, Peng-Qi. 2015. "Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide". United States. doi:10.1016/J.JSSC.2014.12.026.
@article{osti_22475597,
title = {Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide},
author = {Jin, Jun-Cheng and Tong, Wen-Quan and Fu, Ai-Yun and Xie, Cheng-Gen and Chang, Wen-Gui and Wu, Ju and Xu, Guang-Nian, E-mail: xuguangnian@126.com and Zhang, Ya-Nan and Li, Jun and Li, Yong and Yang, Peng-Qi},
abstractNote = {Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2{sub 1} helical chains. While the Nd(III) ions are bridged through μ{sub 2}-HIDC{sup 2−} and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2{sub 1} helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2{sub 1} helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature.},
doi = {10.1016/J.JSSC.2014.12.026},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 225,
place = {United States},
year = 2015,
month = 5
}
  • Five functional coordination polymers (formic-based CPs) namely: ([Cu{sub 2}(CHOO){sub 3}(bibp){sub 2}]·CHOO){sub n} (1), ([Co{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O)n (2), ([Ni{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O){sub n} (3) [Co(CHOO){sub 2}(bbibp)]{sub n} (4) and [Zn(CHOO){sub 2}(bbibp)]{sub n} (5) (bibp=4,4′-bis(imidazolyl)biphenyl, bbibp=4,4′-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N′-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1–3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member betweenmore » the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C–H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.« less
  • Four new lanthanide coordination polymers, [Y(Hnip)(nip)(H{sub 2}O)].H{sub 2}O (1), [Ln(Hnip)(nip)(H{sub 2}O){sub 2}].2H{sub 2}O [Ln=Eu(2), Tb(3)] and [Y(nip){sub 2}].(H{sub 2}4,4'-bpy){sub 0.5} (4) [5-nip=5-nitroisophthalate, 4,4'-bpy=4,4'-bipyridine], have been hydrothermally synthesized and structurally characterized. Compound 1 features novel lanthanide-carboxylate groups chains composed of three samehanded helical strands intersecting each other through hinged lanthanide atoms, and these chains are cross-linked by phenylene moieties of carboxylate ligands into a 2D layer structure. Compounds 2 and 3 are isomorphous, and contain 1D catenanelike Ln-O-C-O-Ln chains, which are interconnected by phenylene moieties into 2D layer structures. Compound 4, however, displays a 3D architecture sustained by strong hydrogen bondingmore » interactions between the protonated 4,4'-bpy and the carboxyl oxygen atom from [Y{sub 2}(nip){sub 4}]{sup 2-} with 2D layer structure, and 4,4'-bpy as the guest molecules exist in bilayer channel. The studies for the thermal stabilities of the four compounds show that compound 4 is more stable than other compounds. Compound 2 emits characteristic red luminescence of Eu{sup 3+} ions at room temperature, and its luminescent lifetime and quantum efficiency has been determined. - Graphical abstract: Four lanthanide 5-nitroisophthalate coordination polymers have been hydrothermally prepared and resent different structures and thermal stabilities and photoluminescence properties.« less
  • Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln{sub 2}(Hpdc){sub 2}(C{sub 2}O{sub 4})(H{sub 2}O){sub 4}]{sub n}·2nH{sub 2}O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H{sub 3}pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H{sub 3}pdc was decomposed into (ox){sup 2−} with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P2{sub 1}/c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groupsmore » to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1–4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities. - Graphical abstract: Four 3D microporous lanthanide coordination polymers with reversible structural interconversion have been synthesized. They exhibit characteristic emission bands of the lanthanide ions and possess great thermal stability. - Highlights: • Four lanthanide coordination polymers have been hydrothermal synthesized. • There is an in situ reaction in 1 in which H{sub 3}pdc was decomposed into (ox){sup 2−} with the Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. • TGA and XRD studies reveal that upon hydration–dehydration, compounds 1–4 undergo a reversible structural interconversion process through a cooling-heating cycle. • Compounds 1–4 exhibit characteristic lanthanide-centered luminescence.« less
  • Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C{sub 6}H{sub 2}O{sub 5})(C{sub 6}H{sub 3}O{sub 5})(H{sub 2}O)]{sub n} (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented.more » - Graphical abstract: A new two-dimensional coordination polymer derived from the in-situ hydrolysis of a furan dimethyl ester with lanthanide(III) ions was obtained in order to study its photophysical behavior when constructed from trivalent Eu and Tb. Quantum yields, lifetime measurements, and singlet/triplet state energies values were obtained. The nature of the material's excited state dynamics is examined and correlated to its structure in order to explain the overall luminescent efficiency of the system. - Highlights: • A new lanthanide–furandicarboxylate coordination polymer is presented. • Eu and Tb compounds display luminescent properties, albeit with low quantum yields. • Photophysical behavior explained through the compound's triplet state and structure. • Nonradiative deactivation of luminescence through high-energy oscillators was noted. • Molecular modeling of the organic moiety was conducted.« less
  • 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 viamore » 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 -}.« less