Uranyl ion complexes with 2, 2′:6′, 2′′-terpyridine-4′-carboxylate. Interpenetration of networks involving "expanded ligands". Issue 41 (4th October 2021)

• Record Type: Journal Article
• Authors: Thuéry, Pierre; Harrowfield, Jack
• Is Part Of: CrystEngComm. Volume 23:Issue 41(2021)
• Page Start: 7305
• Page End: 7313
• Publication Date: 2021-10-04
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/d1ce01215k
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : 2, 2′:6′, 2′′-Terpyridine-4′-carboxylate (tpyc − ) forms both homo- and heterometallic uranyl ion complexes including a chiral, twofold interpenetrated polymer involving the "expanded ligand" Ni(tpyc)2 . Abstract : 2, 2′:6′, 2′′-Terpyridine-4′-carboxylic acid (tpycH) has been used as a ligand in the synthesis of four uranyl ion complexes under solvo-hydrothermal conditions. The homometallic complex [(UO2 )2 (tpyc)(HCOO)(OH)2 ] (1 ) contains additional hydroxide and formate anions generated in situ and it crystallizes as a monoperiodic coordination polymer in which uranyl cations are bound to both the carboxylate group and the terpyridine N3 site. Addition of Pb II gives the heterometallic complex [UO2 Pb(tpyc)(HCOO)2 (OH)(H2 O)2 ] (2 ), in which uranyl is bound to the carboxylate group while lead(ii ) occupies the N3 site, further hydroxide- and formate-bridging resulting in a diperiodic arrangement. Both complexes [UO2 Ni(tpyc)2 (OH)(H2 O)]·NO3 ·1.5H2 O (3 ) and [(UO2 )2 Ni2 (tpyc)4 (O)(H2 O)4 ]·(NO3 )2 ·6H2 O (4 ) contain the neutral, octahedral Ni(tpyc)2 "expanded ligand" unit, the uranyl cations being bound to the divergent carboxylate groups and to bridging hydroxo or oxo groups. Complex 3 crystallizes as a heavily corrugated diperiodic assembly in which hydroxo-bridged dinuclear secondary building units are the nodes of a network of sql topology. Chiral, diperiodic polymers with the same topology but a different shape and which are involved in twofold parallel interpenetration, are formed in 4 .