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A comparison of structural and luminescence properties of lead(II) coordination polymers with isomeric thiophenecarboxylate ligands
Abstract
Two new lead(II) coordination polymers with isomeric thiophenecarboxylates, namely [Pb(2tpCOO)2]n (1) and [Pb(3tpCOO)2(H2O)]n (2) (2tpCOO− = thiophene-2-carboxylate, 3tpCOO− = thiophene-3-carboxylate), were synthesized and characterized. Single crystal X-ray crystallography revealed a distorted pentagonal pyramidal geometry {PbO6} around Pb in 1 and a distorted dodecahedral geometry {PbO8} in 2. The distortion derived from the presence of 6 s2 inert electron pair on lead(II), which was confirmed by DFT calculations. The topological classification of obtained polymers has been performed, disclosing the SP 1-periodic net (4,4)(0,2) and gek1 topology in 1 and 2, respectively. Interactions stabilising crystal structures were also confirmed by Hirshfeld surface analysis. Fluorescence properties allowed to distinguish the type of thiophene-monocarboxylic acid isomers. The luminescence intensity which derived from π → π∗ and/or n → π∗ transitions is higher in 2tpCOOH. Photoluminescent properties of complexes 1 and 2 are much more enhanced in comparison to starting ligands. The emission bands in the complexes can be attributed to the ligand-to-metal charge transfer (LMCT) as a change in the intraligand transitions. Additional low energy emissions with large Stokes shifts appeared and were assigned to the metal-centered (MC) transitions involving s and p lead(II) orbitals, which were also confirmed by DFT calculations. Moreover, both complexes were characterized by infrared spectroscopy and thermal stability analysis.
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Authors (6)
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Mateusz Kowalik mgr
- Institute of Chemistry, Jan Kochanowski University in Kielce
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Joanna Masternak dr
- Institute of Chemistry, Jan Kochanowski University in Kielce
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Bogumiła Kupcewicz
- Faculty of Pharmacy, Collegium Medicum in Bydgoszcz, Nicolaus Copernicus University in Torun´ Department of Inorganic and Analytical Chemistry
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Oleksiy Khavryuchenko
- TMM LLC Kyiv, Ukraine Research and Development Department
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Barbara Barszcz dr hab.
- Institute of Chemistry, Jan Kochanowski University in Kielce
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Details
- Category:
- Articles
- Type:
- artykuł w czasopiśmie wyróżnionym w JCR
- Published in:
-
INORGANICA CHIMICA ACTA
no. 471,
pages 446 - 458,
ISSN: 0020-1693 - Language:
- English
- Publication year:
- 2018
- Bibliographic description:
- Kowalik M., Masternak J., Kazimierczuk K., Kupcewicz B., Khavryuchenko O., Barszcz B.: A comparison of structural and luminescence properties of lead(II) coordination polymers with isomeric thiophenecarboxylate ligands// INORGANICA CHIMICA ACTA. -Vol. 471, (2018), s.446-458
- DOI:
- Digital Object Identifier (open in new tab) 10.1016/j.ica.2017.11.035
- Verified by:
- Gdańsk University of Technology
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