Homochiral 3D coordination polymer with unprecedented three-directional helical topology from achiral precursor: synthesis, crystal structure, and luminescence properties of uranyl succinate metal–organic framework

Wang, Juan; Wei, Zhen; Guo, Fengwan; Li, Chenyang; Zhu, Pengfei; Zhu, Wenxin

doi:10.1039/c5dt02111a

Cited by 22 publications

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References 59 publications

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“…Other elongated dicarboxylic acids suitable for a similar study are the linear aliphatic α,ω-diacids of general formula HOOC–(CH 2 ) n −2 –COOH (H 2 C n ), and it is notable that triple interpenetration has previously been found in the mixed ligand complex [UO 2 (C6)(4,4′-bipy)] . Examples of uranyl complexes with the acids corresponding to n = 4 (succinic) and 5 (glutaric) , are well-known (acids with n < 4 will be disregarded here), and those with the longer molecules, n = 6 (adipic), 7 (pimelic), 8 (suberic), 9 (azelaic), and 10 (sebacic) have been investigated in great detail by Cahill’s group. , The association of these latter ligands with molecules in the bridging bipyridine family, 4,4′-bipyridine, 1,2-bis(4-pyridyl)ethane, and trans -1,2-bis(4-pyridyl)ethylene, was particularly studied, and the various roles assumed by these molecules (uranyl coordination, charge balance, and structure-direction) have been shown to be related to the length matching with the dicarboxylate ligand. , Combination of these long-chain dicarboxylates ( n = 7–10) with the more exotic cucurbiturils has also been explored, the latter macrocycles proving to be either coordinated or enclosed within the lattice . It is notable that although many uranyl complexes with the C n 2– anions crystallize as one-dimensional (1D) or two-dimensional (2D) species, molecular complexes , and three-dimensional (3D) frameworks ,,,, have also been observed.…”

Section: Introductionmentioning

confidence: 99%

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions

Thuéry

Harrowfield

2016

Inorg. Chem.

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Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn; n = 7-10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn(2+), Fe(3+), Co(2+), Ni(2+), and Cu(2+)) and 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C9(2-) and C12(2-), all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)2(C9)3] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra- or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen)3][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10(2-) gives [Ni(bipy)3][(UO2)2(C10)3]·2H2O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen)3][(UO2)2(C10)3]·6H2O (8), [Co(phen)3][(UO2)2(C10)3]·7H2O (9), and [Ni(phen)3][(UO2)2(C10)3]·7H2O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8-10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12(2-), are reported. [UO2(C12)(bipy)] (11) is a neutral 1D species in which bipy chelates the uranyl ion and plays an important role in the packing through π-stacking interactions. Two polymeric units, 1D and 2D, coexist in the complex [Ni(bipy)3][(UO2)2(C12)3][UO2(C12)(H2O)2]·H2O (12); the 2D network has the honeycomb topology, but the hexanuclear rings are markedly convoluted, with local features akin to those in helicates, and the counterions are embedded in intralayer cavities. Emission spectra measured in the solid state show in most cases various degrees of quenching, with intense and well-resolved uranyl emission being observed only for complexes 2 and 11.

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Section: Introductionmentioning

confidence: 99%

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions

Thuéry

Harrowfield

2016

Inorg. Chem.

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“…The great affinity of carboxylic acids and carboxylate anions for uranium ions is well-documented even in strongly coordinating solvents such as alcohols, DMF, or water. It was particularly studied for understanding the migration of U(VI) in the environment through interaction with humic and fulvic acids , or the synthesis of a number of coordination polymers. − From these works, we can hypothesize that during the formation of the stable hemiacetal 12b , the acid 12 is first deprotonated by the strong base i PrO – to form i PrOH and the carboxylate ( o -CHO)-C 6 H 4 -CO 2 ̅ which strongly binds to the uranyl ion in a bidentate way. In such carboxylate species [ o -OHC-C 6 H 4 -(κ 2 -CO 2 )UO 2 X], the coordination of the aldehyde function is prevented, which may slow down the hydride transfer from i PrOH.…”

Section: Resultsmentioning

confidence: 99%

Uranyl(VI) Triflate as Catalyst for the Meerwein–Ponndorf–Verley Reaction

et al. 2021

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Catalytic transformation of oxygenated compounds is challenging in f-element chemistry due to the high oxophilicity of the f-block metals. We report here the first Meerwein−Ponndorf−Verley (MPV) reduction of carbonyl substrates with uranium-based catalysts, in particular from a series of uranyl(VI) compounds where [UO 2 (OTf) 2 ] (1) displays the greatest efficiency (OTf = trifluoromethanesulfonate). [UO 2 (OTf) 2 ] reduces a series of aromatic and aliphatic aldehydes and ketones into their corresponding alcohols with moderate to excellent yields, using i PrOH as a solvent and a reductant. The reaction proceeds under mild conditions (80 °C) with an optimized catalytic charge of 2.3 mol % and KO i Pr as a cocatalyst. The reduction of aldehydes (1−10 h) is faster than that of ketones (>15 h). NMR investigations clearly evidence the formation of hemiacetal intermediates with aldehydes, while they are not formed with ketones.

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“…[37] Several UOFs with aliphatic α,ω-dicarboxylate linkers have been reported, from the groups of Thuéry, [38][39][40][41][42] Cahill, [43][44][45] and others. [46,47] The compositions of these elementary uranyl(VI) UOFs can simplistically be represented as (UO 2…”

Section: +mentioning

confidence: 99%

“…Several UOFs with aliphatic α,ω‐dicarboxylate linkers have been reported, from the groups of Thuéry, [ 38–42 ] Cahill, [ 43–45 ] and others. [ 46,47 ] The compositions of these elementary uranyl(VI) UOFs can simplistically be represented as (UO 2 2+ )(C n 2– ) where C n 2– designates the aliphatic α,ω‐dicarboxylate anion with a total of n carbon atoms, C n 2– ≡ [OOC‐[(CH 2 ) n‐ 2 ]‐COO] 2– . Actual UOF compositions are generally more complex than suggested by this nomenclature, such as when additional ions disrupt the stoichiometry of U VI /C n 2– = 1:1.…”

Section: Introductionmentioning

confidence: 99%

Controlling Cation‐Cation Interactions in Uranyl Coordination Dimers by Varying the Length of the Dicarboxylate Linker

et al. 2020

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The chemistry of linear uranyl(V/VI) dioxo cations, [Oyl–U–Oyl]+/2+, is dominated by coordination of uranium in the equatorial plane. Effects of this constraint were evaluated by experiment and theory for gas‐phase mixed‐valence UV/VI coordination dimers in which uranyl moieties are linked by alkyl dicarboxylates, [(UO2+)(UO22+)(OOC‐(CH2)n‐2‐COO2–)2]– (n = 3–12). Faster O2‐addition to dimers with short linkers n = 3 and 4, vs. n ≥ 5, suggests a structural difference. Computed structures with the shortest linkers have bridging dicarboxylates and nearly parallel, non‐interacting uranyls. Longer linkers, n = 5–7, accommodate uranyl orientations with distinct UV–UVI end‐on cation‐cation interactions (CCIs), whereby Lewis base Oyl from UV coordinates to the acid UVI, denoted as UVOyl···UVI. The dimer structure for n = 8 has a UV–UVI side‐on diamond‐shape CCI, with UVOyl···UVI and UVIOyl···UV interactions. Addition of O2 to the n = 4 and 5 dimers yields [(UO22+)2(OOC‐(CH2)n‐2‐COO2–)2(O2–)]–, with UV oxidized to UVI and O2 reduced to O2–. Whereas O2 can associate to and oxidize the exposed UV center for dimers with n = 3 and 4, the more crowded UV site in the CCI structures inhibits O2 addition. The results demonstrate rational structural control of uranyl‐uranyl bonding and reactivity in small coordination complexes.

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Homochiral 3D coordination polymer with unprecedented three-directional helical topology from achiral precursor: synthesis, crystal structure, and luminescence properties of uranyl succinate metal–organic framework

Cited by 22 publications

References 59 publications

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions

Uranyl(VI) Triflate as Catalyst for the Meerwein–Ponndorf–Verley Reaction

Controlling Cation‐Cation Interactions in Uranyl Coordination Dimers by Varying the Length of the Dicarboxylate Linker

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