US EPA

8783610 

Journal Article 

Pyrrophens: Pyrrole-Based Hexadentate Ligands Tailor-Made for Uranyl (UO22+) Coordination and Molecular Recognition 

Mayhugh, J; Niklas, J; Forbes, M; Gorden, J; Gorden, A 

2020 

Yes 

Inorganic Chemistry
ISSN: 0020-1669
EISSN: 1520-510X 

59 

14 

9560-9568 

English 

32590898 

10.1021/acs.inorgchem.0c00439 

WOS:000552287100013 

Derivatives of a novel pyrrole-containing Schiff base ligand system (called "pyrrophen") are presented which feature substituted phenylene linkers (R-1 = R-2 = H (H2L1); R-1 = R-2 = CH3 (H2L2)) and a binding pocket modeled after macrocyclic species. These ligands bind neutral CH3OH in the solid state through pyrrolic hydrogen-bonding. The interaction of the uranyl cation (UO22+) and H2L1-2 yields planar hexagonal bipyramdial uranyl complexes, while the Cu2+ and Zn2+ complexes were found to self-assemble as dinuclear helicate complexes (M2L2) with H2L1 under identical conditions. The favorable binding of UO22+ over Znprovides insight into the molecular recognition of uranyl over other metal species. Structural features of these complexes are examined with special attention to features of the UO22+ coordination environment which distinguish them from other related salophen and porphyrinoid complexes. 

CATALYTIC-ACTIVITY; X-RAY; COMPLEXES; CATIONS; BINDING; HEXAPHYRIN(1.0.1.0.0.0); REDUCTION; NEPTUNYL; DFT