CuPYDC Metalloligands and Postsynthetic Rearrangement/Metalation as Routes to Bimetallic Uranyl Containing Hybrid Materials: Syntheses, Structures, and Fluorescence
- Department of Chemistry, The George Washington University, 725 21st St. N.W., Washington, DC 20052, United States
Treatment of a molecular copper(II) 2,4-pyridinedicarboxylate metalloligand (CuL1) and a copper(II) 2,3-pyridinedicarboxylate coordination polymer (CuL2) with the uranyl cation (UO22+) under hydrothermal conditions has yielded three new coordination polymers: [(UO2)(H2O)2(C7H3NO4)2Cu] (1), [(UO2)(H2O)2(C7H3NO4)2Cu]·H2O (2), and [(UO2)(OH)(H2O)(C7H3NO4)(C7H4NO4)Cu]·H2O (3). Compound 1 is formed upon the treatment of CuL1 with the uranyl cation to yield a one-dimensional coordination polymer. Compounds 2 and 3 are formed upon the rearrangement of the axially binding carboxylate groups in CuL2 to accommodate the uranyl cation to yield extended three-dimensional and two-dimensional topologies, respectively. Attempts to prepare compounds 1–3 via direct assembly have yet to be successful, suggesting that a prebound Cu(II) metal center may be necessary in the synthesis of these bimetallic coordination polymers. Investigation of the emissive properties and the local geometries of compounds 1–3 suggests that the aromaticity of the ligand may influence energy transfer from the uranyl cation to a Cu(II) metal center, thus tuning uranyl fluorescence.
- Research Organization:
- Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- SC0001089
- OSTI ID:
- 1386634
- Journal Information:
- Crystal Growth and Design, Vol. 14, Issue 8; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory; ISSN 1528-7483
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
Similar Records
Structure-Property Relationships in Lithium, Silver, and Cesium Uranyl Borates
Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses