Abstract
Depending on the counterion, uranyl tricarballylate, UO2(tca)−, is shown to crystallize either as two-dimensional nets or as one-dimensional tubules, all with honeycomb topology and united into higher dimensional assemblies when additional metal cations (AgI, PbII) are present. A regular geometric progression involving ligand reorientation is apparent in the series, with triangular furrows in [H2NMe2][UO2(tca)]·H2O (1) followed by deepening square grooves in [UO2Ag(tca)(H2O)]·0.5H2O (2) and full closure of square tubules in [NH4][(UO2)2Pb(tca)2(NO3)(bipy)].
Highlights
Since the first reports of uranyl-based nanotubular structures in phosphonate complexes by Clearfield et al more than 20 years ago,[1,2,3,4,5] the number of such species has steadily increased and, they are still uncommon, as expected for this linear cation, they appear to be accessible from a variety of ligand classes
The tca3– ligand is here in its rightangled shape, with dihedral angles tca of 87.8(5) and 88.2(7)°, but, instead of generating a 2D lattice, the UO2(tca)– assembly is folded so as to create a tubular 1D polymer directed along the a axis, while retaining the {63} topology
The tubules are further assembled into a 2D lattice parallel to (0 1 0) by centrosymmetric nitrate-bridged PbII dimers (KPI 0.74), an arrangement reminiscent of the bridging of uranyl phosphonate tubules by CuII cations.[8]
Summary
Since the first reports of uranyl-based nanotubular structures in phosphonate complexes by Clearfield et al more than 20 years ago,[1,2,3,4,5] the number of such species has steadily increased and, they are still uncommon, as expected for this linear cation, they appear to be accessible from a variety of ligand classes.
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