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Title: Synthesis, structure and luminescence properties of lanthanide complex with a new tetrapodal ligand featuring salicylamide arms

Abstract

A new tetrapodal ligand 1,1,1-tetrakis{l_brace}[(2'-(2-furfurylaminoformyl))phenoxyl]methyl{r_brace}methane (L) has been prepared and their coordination chemistry with Ln{sup III} ions has been investigated. The structure of {l_brace}[Ln{sub 4}L{sub 3}(NO{sub 3}){sub 12}].H{sub 2}O{r_brace}{sub i}nfinity (Ln=Nd, Eu)] shows the binodal 4,3-connected three-dimensional interpenetration coordination polymers with topology of a (8{sup 6}){sub 3}(8{sup 3}){sub 4} notation. [DyL(NO{sub 3}){sub 3}(H{sub 2}O){sub 2}].0.5CH{sub 3}OH and [ErL(NO{sub 3}){sub 3}(H{sub 2}O) (CH{sub 3}OH)].CH{sub 3}COCH{sub 3} is a 1:1 mononuclear complex with interesting supramolecular features. The structure of [NdL(H{sub 2}O){sub 6}].3ClO{sub 4}.3H{sub 2}O is a 2:1 mononuclear complex which further self-assembled through hydrogen bond to form a three-dimensional supramolecular structures. The result presented here indicates that both subtle variation of the terminal group and counter anions can be applied in the modulation of the overall molecular structures of lanthanide complex of salicylamide derivatives due to the structure specialties of this type of ligand. The luminescence properties of the Eu{sup III} complex are also studied in detail. - Grapical Abstract: We present here a series of zero- to three-dimensional lanthanide coordination structures and luminescence properties of Eu(III) complex of a new tetrapodal ligand.

Authors:
 [1];  [2];  [3];  [1];  [4]
  1. College of Chemistry and Chemical Engineering and State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000 (China)
  2. (China)
  3. School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070 (China)
  4. Department of Chemistry, Liaocheng University, Liaocheng 252000 (China)
Publication Date:
OSTI Identifier:
21372441
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 183; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2009.07.062; PII: S0022-4596(09)00402-2; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMIDES; COORDINATION NUMBER; COORDINATION VALENCES; CRYSTAL STRUCTURE; EUROPIUM COMPLEXES; LIGANDS; LUMINESCENCE; MOLECULAR STRUCTURE; POLYMERS; SALICYLIC ACID; SYNTHESIS; TOPOLOGY; CARBOXYLIC ACIDS; COMPLEXES; EMISSION; HYDROXY ACIDS; MATHEMATICS; ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PHOTON EMISSION; RARE EARTH COMPLEXES; VALENCE

Citation Formats

Song Xueqin, School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, Wen Xiaoguang, Liu Weisheng, E-mail: liuws@lzu.edu.c, and Wang Daqi. Synthesis, structure and luminescence properties of lanthanide complex with a new tetrapodal ligand featuring salicylamide arms. United States: N. p., 2010. Web. doi:10.1016/j.jssc.2009.07.062.
Song Xueqin, School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, Wen Xiaoguang, Liu Weisheng, E-mail: liuws@lzu.edu.c, & Wang Daqi. Synthesis, structure and luminescence properties of lanthanide complex with a new tetrapodal ligand featuring salicylamide arms. United States. doi:10.1016/j.jssc.2009.07.062.
Song Xueqin, School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, Wen Xiaoguang, Liu Weisheng, E-mail: liuws@lzu.edu.c, and Wang Daqi. 2010. "Synthesis, structure and luminescence properties of lanthanide complex with a new tetrapodal ligand featuring salicylamide arms". United States. doi:10.1016/j.jssc.2009.07.062.
@article{osti_21372441,
title = {Synthesis, structure and luminescence properties of lanthanide complex with a new tetrapodal ligand featuring salicylamide arms},
author = {Song Xueqin and School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070 and Wen Xiaoguang and Liu Weisheng, E-mail: liuws@lzu.edu.c and Wang Daqi},
abstractNote = {A new tetrapodal ligand 1,1,1-tetrakis{l_brace}[(2'-(2-furfurylaminoformyl))phenoxyl]methyl{r_brace}methane (L) has been prepared and their coordination chemistry with Ln{sup III} ions has been investigated. The structure of {l_brace}[Ln{sub 4}L{sub 3}(NO{sub 3}){sub 12}].H{sub 2}O{r_brace}{sub i}nfinity (Ln=Nd, Eu)] shows the binodal 4,3-connected three-dimensional interpenetration coordination polymers with topology of a (8{sup 6}){sub 3}(8{sup 3}){sub 4} notation. [DyL(NO{sub 3}){sub 3}(H{sub 2}O){sub 2}].0.5CH{sub 3}OH and [ErL(NO{sub 3}){sub 3}(H{sub 2}O) (CH{sub 3}OH)].CH{sub 3}COCH{sub 3} is a 1:1 mononuclear complex with interesting supramolecular features. The structure of [NdL(H{sub 2}O){sub 6}].3ClO{sub 4}.3H{sub 2}O is a 2:1 mononuclear complex which further self-assembled through hydrogen bond to form a three-dimensional supramolecular structures. The result presented here indicates that both subtle variation of the terminal group and counter anions can be applied in the modulation of the overall molecular structures of lanthanide complex of salicylamide derivatives due to the structure specialties of this type of ligand. The luminescence properties of the Eu{sup III} complex are also studied in detail. - Grapical Abstract: We present here a series of zero- to three-dimensional lanthanide coordination structures and luminescence properties of Eu(III) complex of a new tetrapodal ligand.},
doi = {10.1016/j.jssc.2009.07.062},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 183,
place = {United States},
year = 2010,
month = 1
}
  • Two new lanthanide coordination polymers based on a semirigid bridging thenylsalicylamide ligand ([Ln{sub 2}L{sub 3}(NO{sub 3}){sub 6}]·(C{sub 4}H{sub 8}O{sub 2}){sub 2}){sub ∞} were obtained and characterized by elemental analysis, X-ray diffraction, IR and TGA measurements. The two compounds are isostructure and possess one dimensional trapezoid ladder-like chain built up from the connection of isolated LnO{sub 3}(NO{sub 3}){sub 3} polyhedra (distorted monocapped antisquare prism) through the ligand. The photoluminescence analysis suggest that there is an efficient ligand-to-Ln(III) energy transfer in Tb(III) complex and the ligand is an efficient “antenna” for Tb(III). From a more general perspective, the results demonstrated herein providemore » the possibility of controlling the formation of the desired lanthanide coordination structure to enrich the crystal engineering strategy and enlarge the arsenal for developing excellent luminescent lanthanide coordination polymers. - Graphical abstract: We present herein one dimensional lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display interesting structures but also possess strong luminescence properties. Display Omitted - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit interesting structures. • The luminescent properties of Tb(III) complexes are discussed in detail.« less
  • A dinuclear Ln[sup III]-Cu[sup II] complex with an unusual 2-methyl-2,4,6-tris(trifluoromethyl)-1,3-dioxane-4,6-diolato ligand has been synthesized and characterized structurally. The 1,3-dioxane-4,6-diolato ligand is the product of cycloaddition of 1,1,1-trifluoro-2,2-propanediol to a hexafluoroacetylacetonato ligand promoted by the metal complex.
  • Reaction of Ln(NO{sub 3}){sub 3}.6H{sub 2}O with H{sub 2}L [H{sub 2}L=N,N'-bis(salicylidene)propane-1,2-diamine] gives rise to five new coordination polymers, viz. [Pr(H{sub 2}L)(NO{sub 3}){sub 3}(MeOH)]{sub n} (1) and [Ln(H{sub 2}L){sub 1.5}(NO{sub 3}){sub 3}]{sub n} [Ln=La (2), Eu (3), Sm (4) and Gd (5)]. Crystal structural analysis reveals that H{sub 2}L effectively functions as a bridging ligand forming one-dimensional (1D) chain and two-dimensional (2D) open-framework polymers. Solid-state fluorescence spectra of 3 and 4 exhibit typical red fluorescence of Eu(III) and Sm(III) ions at room temperature while 2 emits blue fluorescence of ligand H{sub 2}L. The lowest triplet level of ligand H{sub 2}L wasmore » calculated on the basis of the phosphorescence spectrum of 5. The energy transfer mechanisms in the lanthanide polymers were described and discussed. - Graphical abstract: Five coordination polymers were synthesized. Given is the perspective view of a H{sub 2}L bridged hexametal ring along the c axis for 2 (La), excitation and emission spectra of 3 (Eu) and 4 (Sm) in the solid state.« less
  • The new semirigid exo-bidentate ligand incorporating furfurysalicylamide terminal groups, namely, 1,4-bis([(2′-furfurylaminoformyl)phenoxyl]methyl)-2,5-bismethylbenzene (L) was synthesized and used as building blocks for constructing lanthanide coordination polymers with luminescent properties. The series of lanthanide nitrate complexes have been characterized by elemental analysis, IR spectroscopy, and X-ray diffraction analysis. The semirigid ligand L, as a bridging ligand, reacts with lanthanide nitrates forming three distinct structure types: chiral noninterpenetrated two-dimensional (2D) honeycomblike (6,3) (hcb, Schläfli symbol 6{sup 3}, vertex symbol 6 6 6) topological network as type I, 1D zigzag chain as type II and 1D trapezoid ladder-like chain as type III. The structural diversitiesmore » indicate that lanthanide contraction effect played significant roles in the structural self-assembled process. The luminescent properties of Eu{sup III}, Tb{sup III} and Dy{sup III} complexes are discussed in detail. Due to the good match between the lowest triplet state of the ligand and the resonant energy level of the lanthanide ion, the lanthanide ions in Eu{sup III}, Tb{sup III} and Dy{sup III} complexes can be efficiently sensitized by the ligand. - Graphical abstract: We present herein six lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display diverse structures but also possess strong luminescence properties. - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit diverse structures. • The luminescent properties of Tb{sup III}, Eu{sup III} and Dy{sup III} complexes are discussed in detail.« less
  • The synthesis of the branched-macrocyclic ligand 1 incorporating two 2,2[prime]-bipyridine units in the macrocycle and two 9-methyl-1,10-phenanthroline units in the branches is described as well as the synthesis and the photophysical properties of its Eu[sup 3+], Tb[sup 3+], and Gd[sup 3+] complexes. These complexes do not decompose in water in contrast to those of the related ligand containing 2,2[prime]-bipyridine instead of 1,10-phenanthroline. They show intense absorption bands in the UV region due to absorption in the ligand. The emission spectra of the [Eu[contained in]1][sup 3+] and [Tb[contained in]1][sup 3+] complexes obtained upon ligand excitation show the usual Eu[sup 3+] andmore » Tb[sup 3+] transitions. The pattern of the emission spectrum of the [Eu[contained in]1][sup 3+] complex allows one to assess a low (presumably C[sub 2]) symmetry as the probable site symmetry of the metal ion in the complex. For [Eu[contained in]1][sup 3+] and [Tb[contained in]1][sup 3+], the metal luminescence excitation spectra in water match the ligand absorption spectra while in methanol the absorption due to the phenanthroline is missing. This suggests that in water the efficiency of the ligand-to-metal energy transfer is similar for the two chromophores while in methanol phenanthroline transfers energy to the metal ion less efficiently than bipyridine. The luminescence quantum yield values in water and methanol confirm this interpretation. The lifetimes of the Eu[sup 3+] and Tb[sup 3+] emitting state indicate that the shielding of the metal ion from solvent molecules is rather inefficient. For the [Tb[contained in]1][sup 3+] complex the lifetimes are temperature dependent which is attributed to the presence of an equilibrium between the metal emitting state and triplet excited states of the ligand; this process is most likely responsible for the low luminescence quantum yields and the oxygen effect on the Tb[sup 3+] luminescence.« less