Uranyl Sulfate Nanotubules Templated by N-phenylglycine

Abstract

The synthesis, structure, and infrared spectroscopy properties of the new organically templated uranyl sulfate Na(phgH+)7[(UO2)6(SO4)10](H2O)3.5 (1), obtained at room temperature by evaporation from aqueous solution, are reported. Its structure contains unique uranyl sulfate [(UO2)6(SO4)10]8− nanotubules templated by protonated N-phenylglycine (C6H5NH2CH2COOH)+. Their internal diameter is 1.4 nm. Each of the nanotubules is built from uranyl sulfate rings sharing common SO4 tetrahedra. The template plays an important role in the formation of the complex structure of 1. The aromatic rings are stacked parallel to each other due to the effect of π–π interaction with their side chains extending into the gaps between the nanotubules.

Successive Crystallization of Organically Templated Uranyl Sulfates: Synthesis and Crystal Structures of [pyH](H3O)[(UO2)3(SO4)4(H2O)2], [pyH]2[(UO2)6(SO4)7(H2O)], and [pyH]2[(UO2)2(SO4)3]

“…Following the description of uranyl molybdate [10][11][12][13][14][15][16] and vanadate [23] frameworks, that of 1 can be described as being constructed of 1 ∞ [(UO2)2(SO4)3] 2− ribbons linked by [(UO2)2(SO4)2(H2O)2] groups (Figure 4b). The 1 ∞ [(UO2)2(SO4)3] 2− ribbons (Figure 4c) are in their turn comprised of C1 and C1′ chains used in the description of nanotubules in the structure of Na(C8H10NO2)7[(UO2)6(SO4)10]•3.5H2O [35]. In 2, the UO7 and SO4 polyhedra also share corners to form a 3 ∞ [(UO2)6(SO4)7(H2O)] 2− framework with a more complex topology (Figure 4d).…”

“…The pyH + cations exhibit the common parallel or perpendicular stacking of aromatic rings, which is clearly seen in Figure 6a,c. The same stacking is suggested to be responsible for templating a much more complex nanotubular structure in Na(C8H10NO2)7[(UO2)6(SO4)10]•3.5H2O [35]. It is possible A commonly addressed question is the effect of the organic species on the composition and topology of inorganic backbones where two opposite opinions have been expressed.…”

In Situ Generation of Organic Peroxide to Create a Nanotubular Uranyl Peroxide Phosphate

“…The chair conformation of hexameric uranyl peroxide phosphate macrocycles promotes their stacking through cation–oxo interactions between the hydrated sodium framework and uranyl oxo groups, which results in a one‐dimensional nanotube‐like topology for the extended crystal structure of NUPP . Despite reports of several inorganic uranyl nanotubular structures within the selenite and sulfate systems, NUPP is the first example of one‐dimensional uranyl peroxide structure that has ever been reported in the literature up to date.…”

Organically Templated Layered Uranyl Molybdate [C3H9NH+]4[(UO2)3(MoO4)5] Structurally Based on Mineral-Related Modular Units

“…Four uranyl compounds with nanotubular (NT) motifs formed by corner sharing between UO 7 bipyramids and TO 4 tetrahedra have been described to date: three uranyl-selenates [42,43] and one uranyl-sulfate [44]. Nanotubules differ both in the diameter and structural topology of their walls.…”

“…[47]. The topology of the smallest nanotubules ( Figure 6a) (Figure 6b) are produced from a similar layered archetype [44]. However, there are no layered "ancestors" for the [(UO 2 ) 10 (SeO 4 ) 17 (H 2 O)] 14− nanotubules (Figure 6c), yet their local topology is similar to those of 3:5 layers, which were found, e.g., in the structure of If we dissect the [(UO 2 ) 3 (SeO 4 ) 5 ] 4− tube, as shown in Figure 6a, the planar projection of the layer (Figure 6d) corresponds to the sequence of chains .…”