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Title: Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties

Abstract

A series of lanthanide-organic complexes based on polyoxometalates (POMs) [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}][W{sub 6}O{sub 19}] (Ln=La(1), Ce(2), Sm(3), Eu(4), Gd(5); DNBA=3,5-dinitrobenzoate; DMF=N,N-dimethylformamide) has been synthesized. These complexes consist of [W{sub 6}O{sub 19}]{sup 2-} and dimeric [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}]{sup 2+} cations. The luminescence properties of 4 are measured in solid state and different solutions, respectively. Notably, the emission intensity increases gradually with the increase of solvent permittivity, and this solvent effect can be directly observed by electrospray mass spectrometry (ESI-MS). The analyses of ESI-MS show that the eight coordinated solvent DMF units of dimeric cation are active. They can move away from dimeric cations and exchange with solvent molecules. Although the POM anions escape from 3D supramolecular network, the dimeric state structure of [Ln{sub 2}(DNBA){sub 4}]{sup 2+} remains unchanged in solution. The conservation of red luminescence is attributed to the maintenance of the aggregated state structures of dimeric cations. - Graphical abstract: 3D POMs-based lanthanide-organic complexes performed the solvent effect on the luminescence property. The origin of such solvent effect can be understood and explained on the basis of the existence of coordinated active sites by the studies of ESI-MS. Highlights: Black-Right-Pointing-Pointer The solvent effect on the luminescence property ofmore » POMs-based lanthanide-organic complexes. Black-Right-Pointing-Pointer ESI-MS analyses illuminate the correlation between the structure and luminescence property. Black-Right-Pointing-Pointer The dimeric cations have eight active sites of solvent coordination. Black-Right-Pointing-Pointer The aggregated state structure of dimer cation remains unchanged in solution. Black-Right-Pointing-Pointer Luminescence associating with ESI-MS is a new method for investigating the interaction of complex and solvent.« less

Authors:
 [1]; ; ; ; ; ;  [1]
  1. Key Laboratory of Polyoxometalate Science of Ministry of Education, College of Chemistry, Northeast Normal University, Changchun, Jilin 130024 (China)
Publication Date:
OSTI Identifier:
22012129
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: . 190; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; CATIONS; COMPLEXES; INTERACTIONS; LUMINESCENCE; MASS SPECTROSCOPY; PERMITTIVITY; RARE EARTHS; SOLIDS; SOLUTIONS; SOLVENTS

Citation Formats

Qun, Tang, Liu Shuxia, E-mail: liusx@nenu.edu.cn, Dadong, Liang, Fengji, Ma, Guojian, Ren, Feng, Wei, Yuan, Yang, and Congcong, Li. Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties. United States: N. p., 2012. Web. doi:10.1016/J.JSSC.2012.02.006.
Qun, Tang, Liu Shuxia, E-mail: liusx@nenu.edu.cn, Dadong, Liang, Fengji, Ma, Guojian, Ren, Feng, Wei, Yuan, Yang, & Congcong, Li. Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties. United States. https://doi.org/10.1016/J.JSSC.2012.02.006
Qun, Tang, Liu Shuxia, E-mail: liusx@nenu.edu.cn, Dadong, Liang, Fengji, Ma, Guojian, Ren, Feng, Wei, Yuan, Yang, and Congcong, Li. Fri . "Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties". United States. https://doi.org/10.1016/J.JSSC.2012.02.006.
@article{osti_22012129,
title = {Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties},
author = {Qun, Tang and Liu Shuxia, E-mail: liusx@nenu.edu.cn and Dadong, Liang and Fengji, Ma and Guojian, Ren and Feng, Wei and Yuan, Yang and Congcong, Li},
abstractNote = {A series of lanthanide-organic complexes based on polyoxometalates (POMs) [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}][W{sub 6}O{sub 19}] (Ln=La(1), Ce(2), Sm(3), Eu(4), Gd(5); DNBA=3,5-dinitrobenzoate; DMF=N,N-dimethylformamide) has been synthesized. These complexes consist of [W{sub 6}O{sub 19}]{sup 2-} and dimeric [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}]{sup 2+} cations. The luminescence properties of 4 are measured in solid state and different solutions, respectively. Notably, the emission intensity increases gradually with the increase of solvent permittivity, and this solvent effect can be directly observed by electrospray mass spectrometry (ESI-MS). The analyses of ESI-MS show that the eight coordinated solvent DMF units of dimeric cation are active. They can move away from dimeric cations and exchange with solvent molecules. Although the POM anions escape from 3D supramolecular network, the dimeric state structure of [Ln{sub 2}(DNBA){sub 4}]{sup 2+} remains unchanged in solution. The conservation of red luminescence is attributed to the maintenance of the aggregated state structures of dimeric cations. - Graphical abstract: 3D POMs-based lanthanide-organic complexes performed the solvent effect on the luminescence property. The origin of such solvent effect can be understood and explained on the basis of the existence of coordinated active sites by the studies of ESI-MS. Highlights: Black-Right-Pointing-Pointer The solvent effect on the luminescence property of POMs-based lanthanide-organic complexes. Black-Right-Pointing-Pointer ESI-MS analyses illuminate the correlation between the structure and luminescence property. Black-Right-Pointing-Pointer The dimeric cations have eight active sites of solvent coordination. Black-Right-Pointing-Pointer The aggregated state structure of dimer cation remains unchanged in solution. Black-Right-Pointing-Pointer Luminescence associating with ESI-MS is a new method for investigating the interaction of complex and solvent.},
doi = {10.1016/J.JSSC.2012.02.006},
url = {https://www.osti.gov/biblio/22012129}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = . 190,
place = {United States},
year = {2012},
month = {6}
}