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Molecular assemblies of a series of mixed tetravalent uranium and trivalent lanthanide complexes associated with the dipicolinate ligand, in aqueous medium

(2018) CRYSTAL GROWTH & DESIGN. 18(4). p.2165-2179
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Abstract
The investigations of the chemical system involving tetravalent uranium associated with trivalent lanthanides (La, Ce, Nd, Sm Er, Lu) and dipicolinic acid (H(2)dpa) led to the identification of six distinct types of heterometallic coordination complexes (I-VI). These compounds, obtained at room temperature from aqueous solution, have been characterized by single crystal X-ray diffraction. They consist of tris-chelated dipicolinate uranium subunits {U(dpa)(3)} interacting with poly oxo/aquo or mixed polyoxo/aquo chelated dipicolinate lanthanide subunits (LnO(1-3)(H(2)0)(5-8) or Ln(dpa)O0-3(H20)(4-6)) in different arrangements. Complex I (La, Ce) exhibits the assembly of molecular dinudear [ULn] and [ULnU] trinuclear units, with a linkage between U and Ln via bidentate carboxylate groups of the dipicolinate molecules. The same carboxylate bridging connection mode creates a linear chainlike coordination polymer in complex II (La, Ce), with a strict alternating U Ln sequence. Complex III (Ce, Nd) contains an octanuclear motif based on six-ring [Ln(4)U(2)] decorated by two peripheral {U(dpa)(3)} subunits, resulting in a [Ln(4)U(4)] entity, through carboxylate bridges. Complex IV crystallizes by using a wide series of lanthanide cations (Nd, Sm-Tb) and consists of a simple assembly of discrete {U(dpa)(3)} subunits with {Ln(Hdpa)(H2O)(6)}. The complex V (Tb Er) is composed of a hexanudear motif based on four-ring [U(2)Ln(2)] with two peripheral {U(dpa)(3)} subunits (final complex [U(4)Ln(2)]). The last complex (VI) occurs with the lutetium and is built up from a dinudear unit [ULu] connected through one carboxylate group. Thermal decomposition of samples of complexes II IV has been analyzed by thermogravimetry and in situ XRD. The luminescence spectrum of the europium-based complex IV has been measured.
Keywords
POLYMETALLIC OXALATO COMPLEXES, NITRIC-ACID SOLUTIONS, COORDINATION POLYMERS, ORGANIC-FRAMEWORK, CRYSTAL-STRUCTURE, 2, 6-PYRIDINEDICARBOXYLIC ACID, URANYL-VANADATE, X-RAY, ND, LN

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Chicago
Martin, Nicolas P, Christophe Volkringer, Natacha Henry, Sylvain Duval, Dimitrije Mara, Rik Van Deun, and Thierry Loiseau. 2018. “Molecular Assemblies of a Series of Mixed Tetravalent Uranium and Trivalent Lanthanide Complexes Associated with the Dipicolinate Ligand, in Aqueous Medium.” Crystal Growth & Design 18 (4): 2165–2179.
APA
Martin, N. P., Volkringer, C., Henry, N., Duval, S., Mara, D., Van Deun, R., & Loiseau, T. (2018). Molecular assemblies of a series of mixed tetravalent uranium and trivalent lanthanide complexes associated with the dipicolinate ligand, in aqueous medium. CRYSTAL GROWTH & DESIGN, 18(4), 2165–2179.
Vancouver
1.
Martin NP, Volkringer C, Henry N, Duval S, Mara D, Van Deun R, et al. Molecular assemblies of a series of mixed tetravalent uranium and trivalent lanthanide complexes associated with the dipicolinate ligand, in aqueous medium. CRYSTAL GROWTH & DESIGN. 2018;18(4):2165–79.
MLA
Martin, Nicolas P, Christophe Volkringer, Natacha Henry, et al. “Molecular Assemblies of a Series of Mixed Tetravalent Uranium and Trivalent Lanthanide Complexes Associated with the Dipicolinate Ligand, in Aqueous Medium.” CRYSTAL GROWTH & DESIGN 18.4 (2018): 2165–2179. Print.
@article{8558426,
  abstract     = {The investigations of the chemical system involving tetravalent uranium associated with trivalent lanthanides (La, Ce, Nd, Sm Er, Lu) and dipicolinic acid (H(2)dpa) led to the identification of six distinct types of heterometallic coordination complexes (I-VI). These compounds, obtained at room temperature from aqueous solution, have been characterized by single crystal X-ray diffraction. They consist of tris-chelated dipicolinate uranium subunits \{U(dpa)(3)\} interacting with poly oxo/aquo or mixed polyoxo/aquo chelated dipicolinate lanthanide subunits (LnO(1-3)(H(2)0)(5-8) or Ln(dpa)O0-3(H20)(4-6)) in different arrangements. Complex I (La, Ce) exhibits the assembly of molecular dinudear [ULn] and [ULnU] trinuclear units, with a linkage between U and Ln via bidentate carboxylate groups of the dipicolinate molecules. The same carboxylate bridging connection mode creates a linear chainlike coordination polymer in complex II (La, Ce), with a strict alternating U Ln sequence. Complex III (Ce, Nd) contains an octanuclear motif based on six-ring [Ln(4)U(2)] decorated by two peripheral \{U(dpa)(3)\} subunits, resulting in a [Ln(4)U(4)] entity, through carboxylate bridges. Complex IV crystallizes by using a wide series of lanthanide cations (Nd, Sm-Tb) and consists of a simple assembly of discrete \{U(dpa)(3)\} subunits with \{Ln(Hdpa)(H2O)(6)\}. The complex V (Tb Er) is composed of a hexanudear motif based on four-ring [U(2)Ln(2)] with two peripheral \{U(dpa)(3)\} subunits (final complex [U(4)Ln(2)]). The last complex (VI) occurs with the lutetium and is built up from a dinudear unit [ULu] connected through one carboxylate group. Thermal decomposition of samples of complexes II IV has been analyzed by thermogravimetry and in situ XRD. The luminescence spectrum of the europium-based complex IV has been measured.},
  author       = {Martin, Nicolas P and Volkringer, Christophe and Henry, Natacha and Duval, Sylvain and Mara, Dimitrije and Van Deun, Rik and Loiseau, Thierry},
  issn         = {1528-7483},
  journal      = {CRYSTAL GROWTH \& DESIGN},
  keyword      = {POLYMETALLIC OXALATO COMPLEXES,NITRIC-ACID SOLUTIONS,COORDINATION POLYMERS,ORGANIC-FRAMEWORK,CRYSTAL-STRUCTURE,2,6-PYRIDINEDICARBOXYLIC ACID,URANYL-VANADATE,X-RAY,ND,LN},
  language     = {eng},
  number       = {4},
  pages        = {2165--2179},
  title        = {Molecular assemblies of a series of mixed tetravalent uranium and trivalent lanthanide complexes associated with the dipicolinate ligand, in aqueous medium},
  url          = {http://dx.doi.org/10.1021/acs.cgd.7b01617},
  volume       = {18},
  year         = {2018},
}

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