MOFs with 12-Coordinate 5f-Block Metal Centers.
J Am Chem Soc
; 144(7): 2879-2884, 2022 Feb 23.
Article
in En
| MEDLINE
| ID: mdl-35143201
ABSTRACT
We have constructed an unprecedented MOF platform that accommodates a range of 5f-block metal ions (Th4+, U4+, Np4+, Pu4+) as the primary building block. The isoreticular actinide metal-organic frameworks (An-MOFs) exhibit periodic trends in the 12-coordinate metal environment, ligand configuration, and resulting ultramicroporosity. It holds potential in distinguishing neighboring tetravalent actinides. The metal ionic radius, carboxylate bite angle, anthracene plane twisting, interligand interactions, and countercation templating collectively determine an interplay between solvation, modulation, and complexation, resulting in a coordination saturation of the central actinide, while lanthanide counterparts are stabilized by the formation of a dimer-based motif. Quantum chemical calculations indicate that this large coordination number is only feasible in the high-symmetry environment provided by the An-MOFs. This category of MOFs not only demonstrates autoluminescence (4.16 × 104 counts per second per gram) but also portends a wide-bandgap (2.84 eV) semiconducting property with implications for a multitude of applications such as hard radiation detection.
Full text:
1
Database:
MEDLINE
Language:
En
Journal:
J Am Chem Soc
Year:
2022
Type:
Article
Affiliation country:
China