Uranyl Complexes as Scaffolding or Spacers for Cucurbit[6]uril Molecules in Homo‐ and Heterometallic Species, Including a Uranyl–Lanthanide Complex. Issue 22 (9th June 2017)

• Record Type: Journal Article
• Authors: Thuéry, Pierre
• Is Part Of: European journal of inorganic chemistry. Issue 22(2017)
• Page Start: 2876
• Page End: 2882
• Publication Date: 2017-06-09
• Subjects: Uranium -- Cucurbiturils -- Structure elucidation -- Heterometallic complexes -- Anion encapsulation; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700283
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The reaction of uranyl nitrate with cucurbit[6]uril (CB6) and carboxylic or sulfonic ligands under hydrothermal conditions and in the presence of additional metal cations (K I or Ce III ) or cosolvents provided four complexes, which were crystallographically characterized. The compound [(UO2 )2 K2 (CB6)(adc)2 (NO3 )2 (H2 O)2 ]· 5H2 O (1 ), where H2 adc is 1, 3‐adamantanedicarboxylic acid, crystallizes in the form of a central K2 (CB6) 2+ column surrounded by two one‐dimensional (1D) polymeric UO2 (adc)(NO3 ) – chains attached to the column by nitrate bridges, with a perfect match of the repeat lengths in the two subunits. The longer 1, 3‐adamantanediacetic acid (H2 adac) gives the complex [(UO2 )2 (adac)2 (HCOOH)2 ]· CB6· 6H2 O (2 ), in which the 1D uranyl‐containing polymer and columns of CB6 molecules form a layered arrangement held by weak CH··· O hydrogen bonds. The complex formed with the dipotassium salt of methanedisulfonic acid (K2 mds), [(UO2 )2 K2 (CB6)(mds)2 (OH)2 (H2 O)8 ]· 4H2 O (3 ), is a 1D polymer, in which K2 (CB6) 2+ units are connected to one another by doubly hydroxide‐bridged uranyl dimers in which the disulfonates are terminal, chelating ligands; connection between the two subunits is solely through potassium oxo‐bonding to uranyl. The complex [(UO2 )2 Ce2 (CB6)(C2 O4 )3 (NO3 )4 (H2 O)6 ]· 2H2 O (4 ) is a 1D polymer containing bridging oxalate ligands formed in situ, in which CB6 is coordinated to the lanthanide cations only; one nitrate ligand and one water ligand, hydrogen‐bonded to each other, are included in the CB6 cavity, with the possible occurrence of interactions between nitrate oxygen atoms and ureido carbon atoms. Abstract : Three dicarboxylic acids and one disulfonic acid were used as ligands to generate four complexes containing uranyl cations and cucurbit[6]uril (CB6) molecules. In no case is uranyl directly bound to CB6; carbonyl groups are coordinated to K I or Ce III when present. One‐dimensional polymers are formed in all cases, and the uranyl‐containing subunits assume various roles in the heterometallic complexes.