Two Three‐Dimensional Actinide–Silver Heterometallic Coordination Polymers Based on 2,2′‐Bipyridine‐3,3′‐dicarboxylic Acid with Helical Chains Containing Dimeric or Trimeric Motifs

Abstract

Under hydrothermal conditions, two new 3D actinide–silver (An–Ag) heterometallic coordination polymers, namely, [Ag(UO2)2(µ2‐OH)(bpdc)2(H2O)2]n (1) and [Ag3Th6(µ3‐O)(µ3‐OH)(µ2‐OH)6(bpdc)6(NO3)6·H2O]n (2, H2bpdc = 2,2′‐bipyridine‐3,3′‐dicarboxylic acid), were assembled through a hard–soft recognition strategy. Compounds 1 and 2 were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction, and infrared spectroscopy. Both compounds are constructed through the bridging of infinite polynuclear An–bpdc chiral helical chains by AgI cations. Compound 2 represents the first ThIV–AgI heterometallic coordination polymer. Furthermore, the thermal stability and luminescence properties of 1 were studied.

1,2,4-Triazolyl-4-acetate: a ditopic ligand combining soft and hard donor sites in homometallic (AgI) and heterometallic (AgI/UVI) coordination polymers

“…Such a synthetic strategy seems to be more rational than those used with previously reported Ag I /U VI coordination polymers, where silver(I) centers serve as a charge-balancing counterion [24][25][26] or play an additional singlenode binding role. [27][28][29][30] The contemporary importance of uranium coordination chemistry concerns both uranium isotope enrichment processing and nuclear waste disposal. 31 Storage of large quantities of waste is not the best solution, but a reasonable alternative strategy can be that of recycling/reprocessing into functional materials for civil or commercial applications.…”

Novel Heterometallic Uranyl-Transition Metal Materials: Structure, Topology, and Solid State Photoluminescence Properties

“…5 For example, Farha et al employed nonplanar organic ligands such as the pseudo-four-fold symmetric linker 4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetryl)tetrabenzoic acid (H 4 TBA-Py) 24 to generate a noninterpenetrated uranyl-containing MOF with a tbo topology and large open cavities (17, 24, and 39 Å) and by using the tritopic 5′-(4-carboxyphenyl)-2′,4′,6′-trimethyl-[1,1′:3′,1′′-terphenyl]-4,4′′-dicarboxylic acid 32 ligand to form a mesoporous U-MOF containing large icosidodecahedral cavities with internal diameters of 50 and 62 Å. Another example, reported by Shi et al, 33 Therein, the nitrogen atoms of the pyridine rings coordinated to the Ag + metal center, and the carboxylates coordinated to the actinides, to provide additional bonding to increase framework dimensionality. In the present study, the 2,2′bipyridine-3,3′-dicarboxylic acid (H 2 L) was employed as the polytopic ligand as it exhibits several moieties where coordination to a metal center is possible, carboxylates and nitrogens from the bipyridine rings.…”

Zero-, mono- and diperiodic uranyl ion complexes with the diphenate dianion: influences of transition metal ion coordination and differential UVI chelation

“…12 These particular ligands generally retain a quasi-planar geometry of the diphenyl moiety, but this is no longer true when the carboxylate substituents are located closer to one another, as in 1,1ʹ-diphenyl-2,2ʹ,6,6ʹ-tetracarboxylate, in which steric crowding results in quasi-perpendicular positioning of the two aromatic rings expected to favour triperiodic arrays, and which has actually been shown to form mono-, di-, and triperiodic uranyl complexes. 13 Although 2,2ʹbipyridine-3,3ʹ-dicarboxylate and 1,1ʹ-diphenyl-6,6ʹ-dinitro-2,2ʹ-dicarboxylate, both with tilted aromatic rings, have also been used in this context, [14][15][16] no uranyl ion complex has yet been reported with the simpler ligand resulting from deprotonation of diphenic acid (1,1ʹ-diphenyl-2,2ʹ-dicarboxylic acid, H2dip). In order to expose the possible coordination modes of this ligand toward the uranyl ion and thus its potential for the creation of new coordination arrays, we have synthesized nine homo-or heterometallic complexes under solvo-hydrothermal conditions in the presence of various cosolvents, coligands and additional cations/counterions.…”

“…and 72.09(16)° in 3, and in both cases one -COOgroup is nearly coplanar with the aromatic ring [ dihedral angles 3.7(4) and 5.9(3)°] while the other is more tilted[39.5(3) and 34.6(4)°]. A zigzag 1D coordination polymer running along [010] is formed in both compounds, with the aromatic groups pointing outward (views with different orientations are shown in Figs.…”