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Title: Rare earth niobate coordination polymers

Abstract

Rare-earth (RE) coordination polymers are infinitely tailorable to yield luminescent materials for various applications. In this paper we described the synthesis of a heterometallic rare-earth coordination compound ((CH 3) 2SO) 3(RE)NbO(C 2O 4) 3 ((CH 3) 2SO) = dimethylsulfoxide, DMSO, (C 2O 2 = oxalate), (RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb). The structure was obtained from single crystal X-ray diffraction of the La analogue. The Nb =O and DMSO terminal-bonding character guides assembly of an open framework structure with noncentrosymmetric RE-coordination geometry, and large spacing between the RE centers. A second structure was observed by PXRD for the smaller rare earths (Dy, Ho, Er, Yb); this structure has not yet been determined. The materials were further characterized using FTIR, and photoluminescence measurements. Characteristic excitation and emission transitions were observed for RE = Nd, Sm, Eu, and Tb. Quantum yield (QY) measurements were performed by exciting Eu and Tb analoges at 394 nm (QY 66%) and 464 nm (QY 71%) for Eu; and 370 nm (QY=40%) for Tb. Finally, we attribute the high QY and bright luminescence to two main structure-function properties of the system; namely the absence of water in the structure, and absence of concentration quenching.

Authors:
 [1];  [2];  [3];  [4];  [5];  [3];  [2];  [3]
  1. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry. Dept. of Physics
  2. Oregon State Univ., Corvallis, OR (United States). Dept. of Physics
  3. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
  4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Microsystem Integration Dept.
  5. Rigaku Oxford Diffraction, The Woodlands, TX (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Oregon State Univ., Corvallis, OR (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
OSTI Identifier:
1421636
Report Number(s):
SAND2017-13471J
Journal ID: ISSN 0022-4596; PII: S0022459617305224
Grant/Contract Number:  
NA0003525; CHE-1606982
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 259; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; lanthanides; rare earths; coordination polymers; luminescence; europium; terbium

Citation Formats

Muniz, Collin N., Patel, Hiral, Fast, Dylan B., Rohwer, Lauren E. S., Reinheimer, Eric W., Dolgos, Michelle, Graham, Matt W., and Nyman, May. Rare earth niobate coordination polymers. United States: N. p., 2018. Web. doi:10.1016/j.jssc.2017.12.034.
Muniz, Collin N., Patel, Hiral, Fast, Dylan B., Rohwer, Lauren E. S., Reinheimer, Eric W., Dolgos, Michelle, Graham, Matt W., & Nyman, May. Rare earth niobate coordination polymers. United States. doi:10.1016/j.jssc.2017.12.034.
Muniz, Collin N., Patel, Hiral, Fast, Dylan B., Rohwer, Lauren E. S., Reinheimer, Eric W., Dolgos, Michelle, Graham, Matt W., and Nyman, May. Wed . "Rare earth niobate coordination polymers". United States. doi:10.1016/j.jssc.2017.12.034. https://www.osti.gov/servlets/purl/1421636.
@article{osti_1421636,
title = {Rare earth niobate coordination polymers},
author = {Muniz, Collin N. and Patel, Hiral and Fast, Dylan B. and Rohwer, Lauren E. S. and Reinheimer, Eric W. and Dolgos, Michelle and Graham, Matt W. and Nyman, May},
abstractNote = {Rare-earth (RE) coordination polymers are infinitely tailorable to yield luminescent materials for various applications. In this paper we described the synthesis of a heterometallic rare-earth coordination compound ((CH3)2SO)3(RE)NbO(C2O4)3 ((CH3)2SO) = dimethylsulfoxide, DMSO, (C2O2 = oxalate), (RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb). The structure was obtained from single crystal X-ray diffraction of the La analogue. The Nb=O and DMSO terminal-bonding character guides assembly of an open framework structure with noncentrosymmetric RE-coordination geometry, and large spacing between the RE centers. A second structure was observed by PXRD for the smaller rare earths (Dy, Ho, Er, Yb); this structure has not yet been determined. The materials were further characterized using FTIR, and photoluminescence measurements. Characteristic excitation and emission transitions were observed for RE = Nd, Sm, Eu, and Tb. Quantum yield (QY) measurements were performed by exciting Eu and Tb analoges at 394 nm (QY 66%) and 464 nm (QY 71%) for Eu; and 370 nm (QY=40%) for Tb. Finally, we attribute the high QY and bright luminescence to two main structure-function properties of the system; namely the absence of water in the structure, and absence of concentration quenching.},
doi = {10.1016/j.jssc.2017.12.034},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 259,
place = {United States},
year = {2018},
month = {1}
}

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Figures / Tables:

Table 1. Table 1.: Crystallographic and refinement data for La-NbO1

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Works referencing / citing this record:

Trapping of Nb V by {XW 9 O 33 } 9- (X = As, Sb): Formation of New Sandwich-Type POM Complexes and Their Solution Behavior : Trapping of Nb
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Crystal structure of poly[tetraaqua-(μ4-oxalato-κ4O,O′:O′′,O′′′)-(μ8-benzene-1,2,4,5-tetracarboxylato-κ8O1:O2:O3:O4:O5:O6:O7:O8)yttrium(III)], C6H5O8Y
journal, July 2018

  • Wen, Zhi-Hui; Zhao, Xiao-Xi; Zhao, Dan
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  • DOI: 10.1515/ncrs-2017-0344