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Abstract Qualitative differences in the reactivity of trivalent lanthanide and actinide complexes have long been attributed to differences in covalent metal‐ligand bonding, but there are few examples where thermodynamic aspects of this relationship have been quantified, especially with U3+and in the absence of competing variables. Here we report a series of dimeric phosphinodiboranate complexes with trivalentf‐metals that show how shorter‐than‐expected U−B distances indicative of increased covalency give rise to measurable differences in solution deoligomerization reactivity when compared to isostructural complexes with similarly sized lanthanides. These results, which are in excellent agreement with supporting DFT and QTAIM calculations, afford rare experimental evidence concerning the measured effect of variations in metal‐ligand covalency on the reactivity of trivalent uranium and lanthanide complexes.
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Luminescent lanthanide probes for cations and anions: Promises, compromises, and caveats
The long luminescence lifetimes and sharp emission bands of luminescent lanthanide complexes have long been recognized as invaluable strengths for sensing and imaging in complex aqueous biological or environmental media. Herein we discuss the recent developments of these probes for sensing metal ions and, increasingly, anions. Underappreciated in the field, buffers and metal hydrolysis influence the response of many responsive lanthanide probes. The inherent complexities arising from these interactions are further discussed.
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- Award ID(s):
- 2203624
- PAR ID:
- 10472970
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Current Opinion in Chemical Biology
- Volume:
- 76
- Issue:
- C
- ISSN:
- 1367-5931
- Page Range / eLocation ID:
- 102374
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.cbpa.2023.102374
