Metal–Organic-Framework-Type 1D-Channel Open Network of a Tetravalent Uranium Trimesate

Volkringer, Christophe; Mihalcea, Ionut; Vigier, Jean-François; Beaurain, A.; Visseaux, Marc; Loiseau, Thierry

doi:10.1021/ic2021963

Cited by 49 publications

(73 citation statements)

References 34 publications

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“…The reactions of these highly substituted lipophilic ligands with UCl 4 in the absence of base led directly to four isolable uranium(IV) chloro complexes [{( R1,R2 ArO) 3 tacn}U IV Cl] ( 14 ). In principle, the reduction of 14 with Na(Hg) or KC 8 should generate the analogous U III species,5h,16 which makes accessible uranium(III) complexes from conveniently available UO 3 · 2H 2 O17 as an “off‐the‐shelf” starting material as opposed to starting from valuable uranium metal (subject to occasional restricted supply) 25. The molecular structures of complexes 14 were determined and confirmed by 1 H NMR and UV/Vis spectroscopy, elemental analyses, SQUID magnetic susceptibility data, and single‐crystal X‐ray analyses.…”

Section: Discussionmentioning

confidence: 99%

Synthesis of Differently Substituted tacn‐Based Ligands: Towards the Control of Solubility and Electronic and Steric Properties of Uranium Coordination Complexes

et al. 2013

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Starting from phenols R1,R2ArOH (5) and the anisole derivative 3,5‐di‐tert‐butyl‐2‐methoxybenzyl bromide (13), a series of new tacn‐based ligands (R1,R2ArOR3)3tacn (2) have been synthesized with substituents of varying bulkiness and electronic nature at the ortho and para positions with respect to the oxygen coordination site. It was observed that these groups not only determine the steric shielding and solubility properties of 2, but also deactivate the reactivity of the phenols in the modified Mannich reaction when electron‐withdrawing groups are introduced at the para position in 5. Treatment of the ligands with UCl4 in thf led to the isolation of four uranium(IV) chloro complexes [{(R1,R2ArO)3tacn}UIVCl] (14), which were characterized by different spectroscopic and physical methods (e.g., 1H NMR, UV/Vis, SQUID), corroborating the +4 oxidation state in 14. Single‐crystal X‐ray structure analyses revealed that 14a·CH2Cl2·CH3CN and 14b·1.25CH2Cl2 crystallize in the chiral, orthorhombic space group P212121 [a = 24.934(3), b = 27.941(3), c = 9.045(1) Å, V = 6302(2) Å3, Z = 4] and the chiral, hexagonal space group P63 [a = 22.097(3), c = 17.941(2) Å, V = 7587(2) Å3, Z = 4], respectively. Interestingly, complexes 14a,b self‐organize in the solid state into homochiral 1D polymeric superstructures as a result of weak intermolecular C–H···Cl contacts.

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Section: Discussionmentioning

confidence: 99%

Synthesis of Differently Substituted tacn‐Based Ligands: Towards the Control of Solubility and Electronic and Steric Properties of Uranium Coordination Complexes

et al. 2013

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“…The compounds have been solvothermally synthesized under autogenous pressure using 23 mL Teflon-lined Parr type autoclaves (type 4746) by using the following chemical reactants: uranium tetrachloride (UCl 4 , obtained from the protocol using the reaction of hexachloropropene with uranium oxide UO 3 , described in the literature [28] ), isophthalic acid (C 8 H 6 O 4 , 1,3-H 2 bdc, Aldrich, 98 %), pyromellitic acid (C 10 H 6 O 8 , H 4 btec, Aldrich, 99 %) and anhydrous N,N-dimethylformamide (C 3 H 7 NO, DMF, Aldrich, 99.8 %). The starting chemical reactants (except UCl 4 ) were commercially available and were used without any further purification.…”

Section: Methodsmentioning

confidence: 99%

“…These led to the production of approximately twenty new structures that were isolated by using various organic ligands (formate, [13] acetate, [14][15][16] glycolate, [17] dipicolinate, [18][19][20] malonate, [21] fumarate, [22] benzoate, [23][24][25] terephthalate, [26,27] 4,4Ј-biphenyldicarboxylate, [26] 2,6-naphthalenedicarboxylate, [26] trimesate [28] ). The structural diversity of tetravalent uranium chemistry was also highlighted by the isolation of different nuclearities of inorganic building units, such as monomers, trimers, [28,[17][18][19][20][21] tetramers, [14][15][16]22] hexamers, [13,22,25,26] decamers, [24] hexadecamers, [24] chains [29] or, more recently, the U 38 poly-oxo cluster. [23] In the present contribution, we extended this systematic study to the use of two new carboxylate ligands, such as isophthalic acid (noted 1,3-H 2 bdc) or pyromellitic acid (or 1,2,4,5-benzentetracarboxylic, noted H 4 btec).…”

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confidence: 99%

Solvothermal Synthesis of Tetravalent Uranium with Isophthalate or Pyromellitate Ligands

et al. 2015

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Three new coordination polymers bearing tetravalent uranium have been isolated with the O‐donor ligands such as isophthalate (1,3‐bdc) or pyromellitate (btec). The compounds 1 and 3 have been solvothermaly synthesized in N,N‐dimethylformamide (DMF). The crystal structure of U(1,3‐bdc)2(DMF) (1) is built up from discrete tricapped trigonal‐primastic UO9 units, for which one carbonyl oxygen atom from DMF is bound to uranium. The connection of the UO9 units with the isophthalate linkers occurs in a chelating and bidentate fashion and gives rise to the formation of a 3D framework, delimiting narrow channels running along the [101] direction. Upon heating, the DMF molecules are removed, generating the second phase U(1,3‐bdc)2 (2) compound, closely related to 1. Indeed, the coordination environment of uranium is reduced to eight with a distorted square‐antiprismatic geometry. This transition induces the relative shrinkage of the network (ΔV = 23 %). The structure of the compound U(btec)(DMF)2 (3) also exhibits a 3D framework composed of an isolated bicapped square‐antiprismatic UO10 unit, for which two carbonyl oxygen atoms from DMF are bonded to uranium. Pyromellitate ensures the connection of the UO10 units through the carboxylate arms in a chelating mode. This results in the formation of a network with diamond‐shaped channels, developed along the c axis and encapsulating the DMF molecules. In contrast to 1, no stable phase is observed upon removing the DMF species by heating.

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“…To design frameworks based on interconnected uranium‐based motifs, we initiated investigations using polydentate carboxylate linkers, such as the trimesate group. With this particular molecule, we recently reported the first three‐dimensional framework based on uranium(IV) cations, which interact with these tritopic molecules to generate a channel‐like open structure 8…”

Section: Introductionmentioning

confidence: 99%

Three‐Dimensional MOF‐Type Architectures with Tetravalent Uranium Hexanuclear Motifs (U₆O₈)

Falaise

Volkringer

Vigier

et al. 2013

Chemistry A European J

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Four metal-organic frameworks (MOF) with tetravalent uranium have been solvothermally synthesized by treating UCl4 with rigid dicarboxylate linkers in N,N-dimethylfomamide (DMF). The use of the ditopic ligands 4,4'-biphenyldicarboxylate (1), 2,6-naphthalenedicarboxylate (2), terephthalate (3), and fumarate (4) resulted in the formation of three-dimensional networks based on the hexanuclear uranium-centered motif [U6O4(OH)4(H2O)6]. This motif corresponds to an octahedral configuration of uranium nodes and is also known for thorium in crystalline solids. The atomic arrangement of this specific building unit with organic linkers is similar to that found in the zirconium-based porous compounds of the UiO-66/67 series. The structure of [U6O4(OH)4(H2O)6(L)6]⋅X (L = dicarboxylate ligand; X = DMF) shows the inorganic hexamers connected in a face-centered cubic manner through the ditopic linkers to build up a three-dimensional framework that delimits octahedral (from 5.4 Å for 4 up to 14.0 Å for 1) and tetrahedral cavities. The four compounds have been characterized by using single-crystal X-ray diffraction analysis (or powder diffraction analysis for 4). The tetravalent state of uranium has been examined by using XPS and solid-state UV/Vis analyses. The measurement of the Brunauer-Emmett-Teller surface area indicated very low values (Langmuir <300 m(2) g(-1) for 1, <7 m(2) g(-1) for 2-4) and showed that the structures are quite unstable upon removal of the encapsulated DMF solvent.

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Metal–Organic-Framework-Type 1D-Channel Open Network of a Tetravalent Uranium Trimesate

Cited by 49 publications

References 34 publications

Synthesis of Differently Substituted tacn‐Based Ligands: Towards the Control of Solubility and Electronic and Steric Properties of Uranium Coordination Complexes

Synthesis of Differently Substituted tacn‐Based Ligands: Towards the Control of Solubility and Electronic and Steric Properties of Uranium Coordination Complexes

Solvothermal Synthesis of Tetravalent Uranium with Isophthalate or Pyromellitate Ligands

Three‐Dimensional MOF‐Type Architectures with Tetravalent Uranium Hexanuclear Motifs (U₆O₈)

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Metal–Organic-Framework-Type 1D-Channel Open Network of a Tetravalent Uranium Trimesate

Cited by 49 publications

References 34 publications

Synthesis of Differently Substituted tacn‐Based Ligands: Towards the Control of Solubility and Electronic and Steric Properties of Uranium Coordination Complexes

Synthesis of Differently Substituted tacn‐Based Ligands: Towards the Control of Solubility and Electronic and Steric Properties of Uranium Coordination Complexes

Solvothermal Synthesis of Tetravalent Uranium with Isophthalate or Pyromellitate Ligands

Three‐Dimensional MOF‐Type Architectures with Tetravalent Uranium Hexanuclear Motifs (U6O8)

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Product

Resources

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Three‐Dimensional MOF‐Type Architectures with Tetravalent Uranium Hexanuclear Motifs (U₆O₈)