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A uranium-based UO2(+)-Mn2+ single-chain magnet assembled trough cation-cation interactions.

Mougel V, Chatelain L, Hermle J, Caciuffo R, Colineau E, Tuna F, Magnani N, de Geyer A, Pécaut J, Mazzanti M - Angew. Chem. Int. Ed. Engl. (2013)

Bottom Line: The 5f-3d heterometallic 1D chains [{[UO2(salen)(py)][M(py)4](NO3)}]n, (M=Cd (1) and M=Mn (2); py=pyridine) are assembled trough cation-cation interaction from the reaction of the uranyl(V) complex [UO2(salen)py][Cp*2Co] (Cp*=pentamethylcyclopentadienyl) with Cd(NO3)2 or Mn(NO3)2 in pyridine.The infinite UMn chain displays a high relaxation barrier of 134±0.8 K (93±0.5 cm(-1)), probably as a result of strong intra-chain magnetic interactions combined with the high Ising anisotropy of the uranyl(V) dioxo group.It also exhibits an open magnetic hysteresis loop at T<6 K, with an impressive coercive field of 3.4 T at 2 K.

View Article: PubMed Central - PubMed

Affiliation: Laboratoire de Reconnaissance Ionique et Chimie de Coordination SCIB, UMR-E3 CEA-UJF, INAC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France) http://inac.cea.fr/Pisp/51/marinella.mazzanti.html.

No MeSH data available.


Related in: MedlinePlus

Mercury view of the structure of 1 (top) and a detail of the core with associated distances and angles (bottom). Hydrogen atoms and cocrystallized solvent molecules omitted for clarity. C grey, O red, Cd cream, N light blue, U green.
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fig01: Mercury view of the structure of 1 (top) and a detail of the core with associated distances and angles (bottom). Hydrogen atoms and cocrystallized solvent molecules omitted for clarity. C grey, O red, Cd cream, N light blue, U green.

Mentions: X-ray diffraction studies of 1 show the presence of alternating layers of NO3− anions and of cationic dimetallic chains {[UO2(salen)(py)][Cd(py)4]}nn+ (Figure 1; see also the Supporting Information, Figure S2). The asymmetric unit of 1 contains three uranium and three cadmium ions, which are crystallographically non-equivalent due to the non-linear arrangement of the UO2+ groups and Cd2+ ions along the chain (Figure 1, bottom). The cationic polymeric chain {[UO2(salen)(py)][Cd(py)4]}n+ is formed by the cation–cation interaction of each uranyl(V) oxo group of [UO2(salen)py]− complexes with a Cd2+ ion. The U-O-Cd angle deviates slightly from linearity and ranges from 161.67° to 175.15°. The uranium atom is heptacoordinated with a slightly distorted pentagonal bipyramidal geometry, with the four donor atoms of the salen ligand situated in the equatorial plane and the two uranyl oxygens in the axial position; the seventh coordination position is occupied by a pyridine nitrogen. The cadmium ion is six coordinated in an octahedral geometry, with the two uranyl(V) oxo groups in apical positions and the four pyridine nitrogens in its equatorial plane. The mean Cd–Oyl distance of 2.28(2) Å, is in the range of those found in a heterobimetallic UVI/CdII carboxyphosphonate networks with Cd2+ ions coordinated to the apical oxygens of the uranyl(VI) moieties16 (Cd-Oyl=2.252(4) Å). The U–Oyl distance in 1 (1.87(2) Å) is in the range of U–Oyl distances found for uranyl(V) oxo groups involved in cation–cation interactions leading to discrete clusters9c, 17 or 1D polymeric chains.14, 18


A uranium-based UO2(+)-Mn2+ single-chain magnet assembled trough cation-cation interactions.

Mougel V, Chatelain L, Hermle J, Caciuffo R, Colineau E, Tuna F, Magnani N, de Geyer A, Pécaut J, Mazzanti M - Angew. Chem. Int. Ed. Engl. (2013)

Mercury view of the structure of 1 (top) and a detail of the core with associated distances and angles (bottom). Hydrogen atoms and cocrystallized solvent molecules omitted for clarity. C grey, O red, Cd cream, N light blue, U green.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4232274&req=5

fig01: Mercury view of the structure of 1 (top) and a detail of the core with associated distances and angles (bottom). Hydrogen atoms and cocrystallized solvent molecules omitted for clarity. C grey, O red, Cd cream, N light blue, U green.
Mentions: X-ray diffraction studies of 1 show the presence of alternating layers of NO3− anions and of cationic dimetallic chains {[UO2(salen)(py)][Cd(py)4]}nn+ (Figure 1; see also the Supporting Information, Figure S2). The asymmetric unit of 1 contains three uranium and three cadmium ions, which are crystallographically non-equivalent due to the non-linear arrangement of the UO2+ groups and Cd2+ ions along the chain (Figure 1, bottom). The cationic polymeric chain {[UO2(salen)(py)][Cd(py)4]}n+ is formed by the cation–cation interaction of each uranyl(V) oxo group of [UO2(salen)py]− complexes with a Cd2+ ion. The U-O-Cd angle deviates slightly from linearity and ranges from 161.67° to 175.15°. The uranium atom is heptacoordinated with a slightly distorted pentagonal bipyramidal geometry, with the four donor atoms of the salen ligand situated in the equatorial plane and the two uranyl oxygens in the axial position; the seventh coordination position is occupied by a pyridine nitrogen. The cadmium ion is six coordinated in an octahedral geometry, with the two uranyl(V) oxo groups in apical positions and the four pyridine nitrogens in its equatorial plane. The mean Cd–Oyl distance of 2.28(2) Å, is in the range of those found in a heterobimetallic UVI/CdII carboxyphosphonate networks with Cd2+ ions coordinated to the apical oxygens of the uranyl(VI) moieties16 (Cd-Oyl=2.252(4) Å). The U–Oyl distance in 1 (1.87(2) Å) is in the range of U–Oyl distances found for uranyl(V) oxo groups involved in cation–cation interactions leading to discrete clusters9c, 17 or 1D polymeric chains.14, 18

Bottom Line: The 5f-3d heterometallic 1D chains [{[UO2(salen)(py)][M(py)4](NO3)}]n, (M=Cd (1) and M=Mn (2); py=pyridine) are assembled trough cation-cation interaction from the reaction of the uranyl(V) complex [UO2(salen)py][Cp*2Co] (Cp*=pentamethylcyclopentadienyl) with Cd(NO3)2 or Mn(NO3)2 in pyridine.The infinite UMn chain displays a high relaxation barrier of 134±0.8 K (93±0.5 cm(-1)), probably as a result of strong intra-chain magnetic interactions combined with the high Ising anisotropy of the uranyl(V) dioxo group.It also exhibits an open magnetic hysteresis loop at T<6 K, with an impressive coercive field of 3.4 T at 2 K.

View Article: PubMed Central - PubMed

Affiliation: Laboratoire de Reconnaissance Ionique et Chimie de Coordination SCIB, UMR-E3 CEA-UJF, INAC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France) http://inac.cea.fr/Pisp/51/marinella.mazzanti.html.

No MeSH data available.


Related in: MedlinePlus