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Varying Structure‐Directing Anions in Uranyl Ion Complexes with Ni(2,2′ : 6′,2′′‐terpyridine‐4′‐carboxylate) 2
Author(s) -
Thuéry Pierre,
Harrowfield Jack
Publication year - 2022
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.202200011
Subject(s) - chemistry , uranyl , carboxylate , crystallography , terpyridine , hydrogen bond , ligand (biochemistry) , inorganic chemistry , hydrothermal synthesis , cationic polymerization , molecule , crystal structure , ion , stereochemistry , hydrothermal circulation , metal , polymer chemistry , biochemistry , receptor , organic chemistry , seismology , geology
2,2′ : 6′,2“‐Terpyridine‐4′‐carboxylic acid (tpycH) reacts with uranyl cations under solvo‐hydrothermal conditions to give [UO 2 (tpyc) 2 ] ⋅ 2H 2 O ( 1 ), a monoperiodic polymer different from that previously reported. In the additional presence of Ni II cations, the Ni(tpyc) 2 “expanded ligand” is formed and the structure of its complexes with the uranyl cation depends on the additional anions present. [(UO 2 ) 2 F 4 (H 2 O) 2 Ni(tpyc) 2 ] ⋅ 2H 2 O ( 2 ) and [UO 2 (mds)(H 2 O)Ni(tpyc) 2 ] ( 3 ), where mds 2− is methanedisulfonate, are monoperiodic polymers in which the fluoride anions are bridging and the mds 2− anions chelating. [(UO 2 ) 4 (NO 3 ) 2 (H 2 O) 4 Ni 5 (tpyc) 10 ](CF 3 SO 3 ) 4 (NO 3 ) 2 ⋅ 7H 2 O ( 4 ) crystallizes as a wide and nearly planar monoperiodic ribbon. [(UO 2 ) 2 (NO 3 ) 2 (chdc)Ni(tpyc) 2 ] ⋅ chdcH 2 ⋅ 2CH 3 CN ( 5 ), where chdc 2− is trans ‐1,4‐cyclohexanedicarboxylate, is a monoperiodic chain including both bridging Ni(tpyc) 2 and chdc 2− ligands, the chains being further assembled into layers through hydrogen bonding to bridging chdcH 2 molecules. Finally, [UO 2 Ni 2 (tpyc) 4 ](I 3 ) 2 ( 6 ) crystallizes as a diperiodic network with sql topology. These results point to the possibility of modulating the structure of cationic uranyl ion complexes with Ni(tpyc) 2 through addition of a wide range of bonding or non‐bonding anions.