Uranyl Ion Complexes with trans‐3‐(3‐Pyridyl)acrylic Acid Including a Uranyl–Copper(II) Heterometallic Framework. Issue 28 (11th August 2014)

• Record Type: Journal Article
• Authors: Thuéry, Pierre; Harrowfield, Jack
• Is Part Of: European journal of inorganic chemistry. Issue 28(2014)
• Page Start: 4772
• Page End: 4778
• Publication Date: 2014-08-11
• Subjects: Heterometallic complexes -- Uranium­ -- Copper -- Coordination polymers -- Structure elucidation -- Luminescence; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201402556
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: As a heterofunctional pro‐ligand with both hard and soft coordination sites, trans ‐3‐(3‐pyridyl)acrylic acid (LH) is of potential interest for the design of heterometallic complexes of f‐ and d‐block cations, as previously shown in the case of lanthanides. The reaction of LH with uranyl nitrate in water/acetonitrile at 180 °C yields the complex [(UO2 )3 (L)(HL)(O)(OH)3 ]· 2.5H2 O· CH3 CN (2 ), which is different from the previously reported complex [UO2 (L)(OH)] (1 ). Complex2 crystallizes as a ribbon‐like 1D coordination polymer with a skeleton bridged by oxido and hydroxido ligands, in which the uranyl cation is bound to the bridging bidentate carboxylato groups, and the pyridyl groups (one of them protonated) are directed sideways. In the presence of copper nitrate, the reaction affords the heterometallic complex [(UO2 )2 Cu(L)3 (O)(H2 O)](NO3 ) (3 ), in which the harder uranium atom is bound to two μ3 ‐oxido anions and to chelating and bridging carboxylato groups to generate a tetranuclear secondary building unit, whereas the softer copper cations are bound to three pyridyl groups and only one carboxylato donor. The copper atoms are further involved in cation–cation interactions with uranyl oxido groups, and the Cu–O(oxido) bond lengths of 2.162(13) and 2.248(16) Å are among the shortest measured to date.3 crystallizes as a 3D assembly, which displays narrow channels, and it illustrates the ability of copper cations, in combination with a ditopic ligand, to assemble discrete uranyl‐containing units into a framework structure. The emission spectra of complexes1 and2 in the solid state display the usual vibronic progression of the uranyl ion in the range 450–650 nm, and the width of the bands indicates that they may be the superposition of slightly different series, due to the inequivalent uranyl centres in the lattices. Abstract : The heterofunctional pro‐ligand trans ‐3‐(3‐pyridyl)acrylic acid was used to build a uranyl–copper(II) heterometallic complex, in which the preferential bonding of the two cations reflects hard and soft affinities and which crystallizes as a 3D framework. The crystal structure of a new 1D homometallic uranyl complex with the same ligand is also described.