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High Nuclearity Uranyl Cages Using Rigid Aryl Phosphonate Ligands
Author(s) -
Adelani Pius O.,
Sigmon Ginger E.,
Szymanowski Jennifer E. S.,
Burns Peter C.
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900953
Subject(s) - phosphonate , chemistry , uranyl , ligand (biochemistry) , aryl , crystallography , yield (engineering) , stereochemistry , polymer chemistry , combinatorial chemistry , organic chemistry , ion , biochemistry , alkyl , receptor , materials science , metallurgy
Two high nuclearity uranyl cages were crystallized in high yield under mild solvothermal conditions using rigid aryl phosphonate ligands. These compounds are prepared either through an in situ phosphonate ligand condensation reaction or via serendipitous assembly with a bulky phosphonate ligand. Firstly, the flexibility of the phosphonate ligands enhances the curvature of the uranyl polyhedra in the assembly of both compounds. Secondly, the formation of bent pyrophosphonate ligands through temperature and solvent‐driven in situ ligand synthesis is crucial for the assembly of UPhPO 3 . Thirdly, the serendipitous assembly of UPh 2 CPO 3 is favored by the use of sterically hindered bulky phosphonate ligands. The overall structure of UPhPO 3 consists of 16 uranyl cations that are coordinated by phenyl phosphonate and pyrophosphonate ligands while UPh 2 CPO 3 structure is built from uranyl dimers and bulky fluorenyl phosphonate ligand to yield a 12 membered cage.