Directed Synthesis of {Mn₁₈Cu₆} Heterometallic Complexes

Abstract

A two‐step method for the directed synthesis of high‐nuclearity MnIII‐MnII‐CuII heterometallic transition metal complexes is described. The synthesis starts from a preformed copper(II) complex to trap an inner hexacapped cuboctahedral manganese oxide core.

A ferromagnetically coupled Fe42 cyanide-bridged nanocage

“…First, 12 Fe III-HS centres in {Fe(NC) 4 (dpp)(H 2 O)} units are defined as the vertices of cuboctahedron, all of whose sides have a length of 7.85 Å. Second, six square windows of the cuboctahedron are stellated with 24 isosceles triangles, each with side lengths of 6.83, 6.83 and 7.85 Å, with six vertices defined by Fe III-HS ions from {Fe(NC) 4 (H 2 O) 2 } units3435. The Fe II – CN – Fe III linkage of 1 ·18H 2 O classify it as a Prussian blue analogue3637 from the standpoint of its electronic state.…”

Enhancement of TbIII–CuII Single‐Molecule Magnet Performance through Structural Modification

“…The ability displayed by bis–tris propane (H 6 L) to direct the synthesis of Cu/3d heterometallic complexes presented in previous work (3d=Mn(II/III), Zn(II)) makes it a very attractive candidate for exploring the reactivity of the {Cu(H 6 L)} units with magnetically more interesting metal ions, such as rare earth elements. Therefore, several experiments involving different copper and lanthanide salts have been performed in order to study the reactivity of H 6 L in the presence of Ln III ions.…”

“…Given the previously reported 3d,3d′ heterometallic compounds with H 6 L, the importance of Cu II ions in the synthetic procedure is significant. In such complexes, the Cu II atoms occupy the internal {N 2 O 2 } pocket of the ligand to the detriment of other 3d ions present in the reaction media (e.g., Mn, Zn), and thus direct and control the final molecular assembly . In addition, Cu II ions display a flexible coordination geometry and a strong ferromagnetic tendency in Cu⋅⋅⋅4f interactions for the heavier Ln ions .…”

Synthesis and Magnetic Properties of a Series of Octanuclear [Fe6Ln2] Nanoclusters

“…26-31 {(CH 2 OH) 3 CNH(CH 2 ) 3 NHC(CH 2 OH) 3 } (Bis-tris propane, H 6 L), a promising candidate with N 2 O 6 donor set, has been well utilized to fabricate 3d, 3d-3d, 4f clusters, [32][33][34][35] however, 3d-4f multinuclear complexes based on Bis-tris propane has never been documented until now. Furthermore, it has also been proved that flexible ligands can adopt diverse conformations according to the geometric requirements of metal ions, which may result in unexpected and fascinating structures such as polynuclear-based frameworks, novel topologies and chiral networks.…”