A New Preorganized Metalloligand Linker for the Construction of Luminescent Coordination Polymers

Abstract

(3), and [Mn(UO 2 )(bptc)(H 2 O) 3 ] n (4) (H 4 bptc = 2,2′-bipyridine-3,3′,6,6′-tetracarboxylic acid), has been successfully synthesized by assembly of the preorganized metalloligand motifs [(UO 2 )(bptc)] 2− and the corresponding metal salts under hydrothermal conditions. The structural analysis reveals that compound 1 features the assembly of a cationic chain and an anionic chain to form a one-dimensional (1D) double-stranded structure. Isostructural compounds 2 and 3 possess the same three-dimensional (3D) frameworks with (2 ) topology built from the connection of the [UO 2 (bptc)] n 2n− chain with uranyl ions and the corresponding Cd(II)/Zn(II) centers. Compound 4 exhibits a 3D framework with a point symbol of (4 2 •6 5 • 8 3 )(4 2 •6) and is constructed by the [UO 2 (bptc)] n 2n− chain with the 3-connected Mn(II) centers. Interestingly, compounds 1−3 exhibit strong photoluminescence in the visible region that can be divided into two sets of characteristic uranyl emissions, which indicates that the metalloligand motif [(UO 2 )(bptc)] 2− could be an effective luminescent center for the construction of luminescent coordination polymers. In addition, the thermal stabilities of compounds 1−4 have also been investigated.

Filling the equatorial garland of uranyl ion: its content and limitations

“…6). The disordered H2dabco 2+ cations, located between [43], where chelation of the bipyridine unit between two carboxylates is associated with significantly shorter U-N bond lengths than in simple bipyridine complexes [58] where the coordination number and coordination sphere composition are the same.…”

“…and another is that for carboxylato complexes in particular it is best known for uranyl centres forming part of neutral, infinite polymer chains where the equatorial coordination is due to four 2- 1 O, 1 O' bridging carboxylate units[6,[39][40][41][42][43], although, as noted above, there are precedents[37] for the present observation of a mononuclear species. As well, U(VI) in…”

Luminescent uranium–thiophene dicarboxylate frameworks supported by transition-metal–organic cations: dimensionality and luminescence control in uranyl speciation

“…. Most reuse of uranium is based on its coordination with organic ligands (including polycarboxylates, phosphates, germanates, arsenates and molybdates) to generate uranyl-organic frameworks (UOFs), [2][3][4] which have exhibited many promising applications such as in luminescent materials, 5,6 photocatalytic degradation of organic pollutants, 7,8 chemical sensors, 9,10 photoelectric conversion, 11 and so on. Among the various organic ligands, polycarboxylates can demonstrate versatile coordinated modes and remarkable functional properties.…”

A 3D-Coordination Polymer Assembled from Copper Propionate Paddlewheels and Potassium Propionate 1D-Polymeric Rods Possessing a Temperature-Driven Single-Crystal-to-Single-Crystal Phase Transition

“…X-ray-quality single crystals of [HKCu 2 Prop 6 ] were obtained via slow crystallization from the hot solution in concentrated HProp containing copper and potassium atoms in the same stoichiometry as was used in the synthesis of the bulk sample (4 ] were performed on a Bruker D8 QUEST diffractometer with a Photon III CMOS area detector using Mo Kα radiation (λ = 0.71073 Å, graphite monochromator) in the temperature range 100−298 K upon both cooling and heating the single crystals, which were the same in all measurements for the specific compound. Full diffraction experiments were carried out at 100, 150, 180, and 220 K for [HKCu 2 Prop 6 ] and at 100, 130, 150, 180, 210, 240, 270, and 298 K for [Cu 2 (H 2 O) 2 Prop 4 ] to perform the crystal structure solution and refinement.…”

“…In the recent decades, the development of coordination polymers has become one of the critically important areas of coordination chemistry, since these are of extremely high scientific value due to their unusual functional properties (luminescence, − magnetism, − catalysis, − etc.) The design of coordination polymers with different structural topologies (including low-dimensional 1D-chain and 2D-layered motifs) is being developed in great strides.…”