Journal article
Probing the Influence of N-Donor Capping Ligands on Supramolecular Assembly in Molecular Uranyl Materials
European journal of inorganic chemistry, Vol.2016(1), pp.126-137
01/2016
DOI: 10.1002/ejic.201501118
Abstract
The syntheses and crystal structures of six new compounds containing the UO22+ cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2′-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2′:6′,2-terpyridine (terpy), 4′-chloro-2,2′:6′,2-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. Supramolecular assembly by halogen and hydrogen bonding as well as π-π interactions is explored in the solid state for six compounds containing the UO22+ cation. Additionally, the effects of the electron-donating ability of the capping ligand on the corresponding luminescence and vibrational spectra of these compounds were investigated.
Details
- Title: Subtitle
- Probing the Influence of N-Donor Capping Ligands on Supramolecular Assembly in Molecular Uranyl Materials
- Creators
- Korey P Carter - Department of Chemistry, The George Washington University, 800 22nd Street NW, Washington, D.C. 20052, United States, http://www.gwu.edu/~cahill/Mark Kalaj - Department of Chemistry, The George Washington University, 800 22nd Street NW, Washington, D.C. 20052, United States, http://www.gwu.edu/~cahill/Christopher L Cahill - Department of Chemistry, The George Washington University, 800 22nd Street NW, Washington, D.C. 20052, United States, http://www.gwu.edu/~cahill/
- Resource Type
- Journal article
- Publication Details
- European journal of inorganic chemistry, Vol.2016(1), pp.126-137
- Publisher
- WILEY-VCH Verlag
- DOI
- 10.1002/ejic.201501118
- ISSN
- 1434-1948
- eISSN
- 1099-0682
- Number of pages
- 12
- Language
- English
- Date published
- 01/2016
- Academic Unit
- Chemistry
- Record Identifier
- 9984216616602771
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