Copper Lanthanide Phosphonate Cages: Highly Symmetric {Cu3Ln9P6} and {Cu6Ln6P6} Clusters with C3v and D3h Symmetry

Moreno‐Pineda, Eufemio; Heesing, Christian; Tuna, Floriana; Zheng, Yan‐Zhen; McInnes, Eric J. L.; Schnack, Jürgen; Winpenny, Richard E. P.

doi:10.1021/acs.inorgchem.5b00649

Cited by 21 publications

(7 citation statements)

References 59 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The cations found here are conventional. The cobalt hexakis(acetonitrile) [Co(NCMe) 6 ] 2+ cation seen in 2a is known to crystallize with small-molecule anions. − Other cobalt and nickel cations have been seen to crystallize with large antimony oxo-clusters. , The copper(I) cation [Cu(NCMe) 4 ] + in 2c is well-known. − The cuprous oxide used in the synthesis of 2c provides an easy way to obtain the Cu + ion in solution (eq 4) . The 19 F NMR spectrum of the Bi 4 O 2 clusters showed only one fluorine resonance, indicating that the trifluoroacetate ligands are exchanging on the NMR time scale.…”

Section: Resultsmentioning

confidence: 99%

“…72,73 The copper (I) cation [Cu(NCMe) 4 ] + in 2c is a well-known. [74][75][76][77][78][79][80] The cuprous oxide used in the synthesis of 2c provides an easy way to obtain the Cu + ion in solution (Equation 4). 81 The These compounds can be described as "butterfly-shaped" with the two central Bi atoms being the hinge atoms of the butterfly and the two end Bi atoms as the wingtip atoms.…”

Section: Anionic Bi 4 ( 3 -O) 2 Compoundsmentioning

confidence: 99%

See 1 more Smart Citation

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

et al. 2016

View full text Add to dashboard Cite

Six new anionic bismuth-oxido clusters containing trifluoroacetate ligands were prepared. These include two new BiO clusters: [M(NCMe)(HO)][Bi(μ-O)(μ-OH)(CFCO)] with an octahedral BiO(OH) core (M = Ni, 1a; Co, 1b) and four BiO clusters, {[Co(NCMe)][Bi(μ-O)(CFCO)]} (2a), {[Co{HC(MeCO)(MeCNH)}][Bi(μ-O)(CFCO)]·2[CFCO]·2[CFCOH]·2[HO]} (2b), {[Cu(NCMe)][Bi(μ-O)(CFCO)]·2[CFCOH]} (2c), and {[MeN][Bi(μ-O)(CFCO)]·2[CFCOH]} (2d). These are among the first bismuth-oxido anionic clusters synthesized, and the first to have transition metal countercations. The BiO anion in 1a and 1b is a high-symmetry octahedron. Additionally, two of the new BiO clusters are arranged in 1D polymeric structures via bridging carboxylate ligands. The cation in compound 2c had not been previously characterized and was also observed in the synthesis of [Co{HC(MeCO)(MeCNH)}][Bi(NO)] (3). The new compounds were characterized using single crystal X-ray crystallography and elemental analysis.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Anionic Bi 4 ( 3 -O) 2 Compoundsmentioning

confidence: 99%

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Polynuclear 3d–4f metal complexes, including metallacrowns, have been attracting attention, because of their interesting properties, such as non-trivial magnetic behavior, − catalytic activity, luminescence, , possibility to serve as recognition agents, , and their use in sensors. , Such complexes could also be considered to be promising for the generation of multifunctional materials. − …”

Section: Introductionmentioning

confidence: 99%

High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown-5 Complexes (Ln^III = Pr, Nd, Sm, Eu)

et al. 2017

View full text Add to dashboard Cite

Complexes {[LnCu(GlyHA)(m-bdc)(HO)][LnCu(GlyHA)(SO)(m-bdc)(HO)]}·(30 + 2x)HO (where GlyHA = glycinehydroxamate, m-bdc = m-phthalate; Ln = Pr and x = 0.21 for compound 1, or Ln = Sm and x = 0.24 for 3) and one-dimensional (1D) coordination polymers {[NdCu(GlyHA)(HO)(m-bdc)]n[NdCu(GlyHA)(HO)(μ-CO)(m-bdc)]}·13nHO (2) and {[EuCu(GlyHA)(HO)](m-bdc)[EuCu(GlyHA)(m-bdc)(HO)]}·17nHO (4) were obtained starting from the 15-metallacrown-5 complexes {[LnCu(GlyHA)(SO)(HO)]}(SO)·6HO (Ln = Pr, Nd, Sm, Eu) by the partial or complete metathesis of sulfate anions with m-phthalate. Compounds 1 and 3 contain unprecedented quadruple-decker neutral metallacrown assemblies, where the [LnCu(GlyHA)] cations are linked by m-phthalate dianions. In contrast, in complexes 2 and 4, these components assemble into 1D chains of coordination polymers, the adjacent {[NdCu(GlyHA)(HO)(m-bdc)]} 1D chains in 2 being separated by discrete [NdCu(GlyHA)(HO)(μ-CO)(m-bdc)]} complex anions. The crystal lattices of 2 and 4 contain voids filled by solvent molecules. Desolvated 4 is able to absorb up to 0.12 cm/g of methanol vapor or 0.04 cm/g of ethanol at 293 K. The isotherm for methanol absorption by compound 4 is consistent with a possible "gate opening" mechanism upon interaction with this substrate. The χT vs T data for complexes 1-4 and their simpler starting materials {[LnCu(GlyHA)(SO)(HO)]}(SO)·6HO (Ln(III) = Pr, Nd, Sm, Eu) were fitted using an additive model, which takes into account exchange interactions between lanthanide(III) and copper(II) ions in the metallamacrocycles via a molecular field model. The exchange interactions between adjacent Cu(II) ions in metallacrown fragments were found to fall in the range of -47 < J < -63 cm. These complexes are the first examples of a Ln(III)-Cu(II) 15-metallacrowns-5 (Ln(III) = Pr, Nd, Sm, Eu), for which values of exchange parameters have now been reported.

show abstract

“…Based on the above considerations, various 3d‐Ln III cluster‐based‐CPs, serving as molecular magnetic refrigerants, have been extensively synthesized and investigated (Tables and ),68–110,113 including Mn–Ln, Co–Ln, Ni–Ln, Cu–Ln, Cr–Ln, Fe–Ln, and Zn–Ln.…”

Section: Recent Advances In Coordination‐cluster‐based Molecular Magnmentioning

confidence: 99%

Coordination‐Cluster‐Based Molecular Magnetic Refrigerants

Zhang

Cheng

2016

The Chemical Record

100

View full text Add to dashboard Cite

Coordination polymers serving as molecular magnetic refrigerants have been attracting great interest. In particular, coordination cluster compounds that demonstrate their apparent advantages on cryogenic magnetic refrigerants have attracted more attention in the last five years. Herein, we mainly focus on depicting aspects of syntheses, structures, and magnetothermal properties of coordination clusters that serve as magnetic refrigerants on account of the magnetocaloric effect. The documented molecular magnetic refrigerants are classified into two primary categories according to the types of metal centers, namely, homo- and heterometallic clusters. Every section is further divided into several subgroups based on the metal nuclearity and their dimensionalities, including discrete molecular clusters and those with extended structures constructed from molecular clusters. The objective is to present a rough overview of recent progress in coordination-cluster-based molecular magnetic refrigerants and provide a tutorial for researchers who are interested in the field.

show abstract

Copper Lanthanide Phosphonate Cages: Highly Symmetric {Cu₃Ln₉P₆} and {Cu₆Ln₆P₆} Clusters with C_3v and D_3h Symmetry

Cited by 21 publications

References 59 publications

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown-5 Complexes (Ln^III = Pr, Nd, Sm, Eu)

Coordination‐Cluster‐Based Molecular Magnetic Refrigerants

Contact Info

Product

Resources

About

Copper Lanthanide Phosphonate Cages: Highly Symmetric {Cu3Ln9P6} and {Cu6Ln6P6} Clusters with C3v and D3h Symmetry

Cited by 21 publications

References 59 publications

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown-5 Complexes (LnIII = Pr, Nd, Sm, Eu)

Coordination‐Cluster‐Based Molecular Magnetic Refrigerants

Contact Info

Product

Resources

About

Copper Lanthanide Phosphonate Cages: Highly Symmetric {Cu₃Ln₉P₆} and {Cu₆Ln₆P₆} Clusters with C_3v and D_3h Symmetry

High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown-5 Complexes (Ln^III = Pr, Nd, Sm, Eu)