Plumbing the uncertainties of solvothermal synthesis involving uranyl ion carboxylate complexes

Abstract

Some of the uncertainties inherent to solvo-hydrothermal synthetic methods which often hinder isolation of the desired product are discussed and illustrated by the structural characterisation of four uranyl ion complexes...

Ni(2,2′:6′,2″-Terpyridine-4′-carboxylate)2 Zwitterions and Carboxylate Polyanions in Mixed-Ligand Uranyl Ion Complexes with a Wide Range of Topologies

“…The uninodal coordination polymer formed is diperiodic and parallel to (100), and it has the {8 2 .10} point symbol and the KIa topological type. The same topology has previously been found in other uranyl ion complexes with elongated ligands such as glutarate, 76 1,13-tridecanedioate, 77 and 1,15-pentadecanedioate. 78 The layers are very thick (∼22 Å), and they display two sets of UO 2 (1,3-pda) polymers on both surfaces, another set of such a polymer in the center, and the bridging Ni(tpyc) 2 units in between.…”

Varying Structure‐Directing Anions in Uranyl Ion Complexes with Ni(2,2′ : 6′,2′′‐terpyridine‐4′‐carboxylate)2

“…[UO 2 (tpyc) 2 ] ⋅ 2H 2 O (1) : tpycH (14 mg, 0.05 mmol), [UO 2 (NO 3 ) 2 (H 2 O) 2 ] ⋅ 4H 2 O (13 mg, 0.026 mmol), and CsNO 3 (20 mg, 0.10 mmol) were dissolved in a mixture of water (0.8 mL), acetonitrile (0.2 mL), and N,N ‐dimethylformamide (0.2 mL), giving a few yellow crystals of complex 1 within two months. As frequently found in solvothermal synthesis involving different metal cations, [12] the Cs + cations, added so as to possibly form a heterometallic complex, are not included in the final compound.…”

Triple-armed aliphatic tricarboxylic acids as sources of ligands for uranyl ion: influence of bridgehead functionalization

“…The complex [H 2 NMe 2 ][UO 2 (tcenm)]·3H 2 O ( 1 ) includes dimethylammonium counterions formed from hydrolysis of the organic cosolvent N , N -dimethylformamide, as very commonly observed, 24 and the 1 : 1 metal/ligand stoichiometry used during the synthesis is retained in the solid state. The uranyl ion is tris-κ 2 O , O ′-chelated by three carboxylate groups from three tcenm 3− ligands [U–O(oxo), 1.763(3) and 1.769(3) Å; U–O(carboxylate), 2.440(2)–2.496(2) Å] (Fig.…”