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Coordination-induced emission enhancement in copper(I) iodide coordination polymers supported by 2-(alkylsulfanyl)pyrimidines.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 7/14/2021, Vol. 50 Issue 26, p9317-9330, 14p
- Publication Year :
- 2021
-
Abstract
- First examples of copper(I) complexes with 2-(alkylsulfanyl)pyrimidine ligands have been synthesized. Reactions of copper(I) iodide with 2-(methylsulfanyl)pyrimidine (L<superscript>1</superscript>) in various metal-to-ligand molar ratios in MeCN afford a ladder-type coordination polymer [Cu<subscript>2</subscript>L<superscript>1</superscript>I<subscript>2</subscript>]<subscript>n</subscript> with polymeric chains built from double-stranded (Cu<subscript>2</subscript>I<subscript>2</subscript>)<subscript>n</subscript> ribbons supported on both sides by μ<subscript>2</subscript>-N,S-L<superscript>1</superscript> molecules. Although the second ligand, 2-(ethylsulfanyl)pyrimidine (L<superscript>2</superscript>), differs from L<superscript>1</superscript> only by a methylene group, its reactions with copper(I) iodide in MeCN yield not only a congenerous coordination polymer, [Cu<subscript>2</subscript>L<superscript>2</superscript>I<subscript>2</subscript>]<subscript>n</subscript> , but also [CuL<superscript>2</superscript>I]<subscript>n</subscript> , in which a similar (Cu<subscript>2</subscript>I<subscript>2</subscript>)<subscript>n</subscript> ribbon is decorated by N-monodentate L<superscript>2</superscript> molecules. Absorption spectra of all compounds represent an interplay of metal + iodine-to-ligand charge transfer (XMLCT) and ligand-centered (LC) and cluster-centered (CC) transitions, while the emission occurs from the excited states of XMLCT nature. The luminescence of [Cu<subscript>2</subscript>L<superscript>1</superscript>I<subscript>2</subscript>]<subscript>n</subscript> and [Cu<subscript>2</subscript>L<superscript>2</superscript>I<subscript>2</subscript>]<subscript>n</subscript> is blue-shifted and greatly enhanced in comparison with that of [CuL<superscript>2</superscript>I]<subscript>n</subscript> (quantum yields: 89% and 68% for [Cu<subscript>2</subscript>L<superscript>1</superscript>I<subscript>2</subscript>]<subscript>n</subscript> and [Cu<subscript>2</subscript>L<superscript>2</superscript>I<subscript>2</subscript>]<subscript>n</subscript> vs. 23% for [CuL<superscript>2</superscript>I]<subscript>n</subscript> at 77 K), which can be associated with a more rigid μ<subscript>2</subscript>-N,S coordination of 2-(alkylsulfanyl)pyrimidine ligands in [Cu<subscript>2</subscript>L<superscript>1</superscript>I<subscript>2</subscript>]<subscript>n</subscript> and [Cu<subscript>2</subscript>L<superscript>2</superscript>I<subscript>2</subscript>]<subscript>n</subscript> leading to a less distorted T<subscript>1</subscript> state. [ABSTRACT FROM AUTHOR]
- Subjects :
- COORDINATION polymers
COPPER
PYRIMIDINES
IODIDES
METHYLENE group
EXCITED states
Subjects
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 50
- Issue :
- 26
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 151265621
- Full Text :
- https://doi.org/10.1039/d1dt00826a