Directed Synthesis of {Mn₁₈Cu₆} Heterometallic Complexes

Abstract

Eine zweistufige Methode für die gezielte Synthese von vielkernigen heterometallischen MnIII‐MnII‐CuII‐Übergangsmetallkomplexen wird beschrieben. Die Synthese geht von einem Kupfer(II)‐Komplex aus, um einen sechsfach überdachten kuboktaedrischen Manganoxid‐Kern einzuschließen.

Anion‐Templated Assembly and Magnetocaloric Properties of a Nanoscale {Gd38} Cage versus a {Gd48} Barrel

“…As depicted in Figure 4, the discrete anion of complex 2 is arranged as a nanoscale barrel containing 48 Gd 3 + , six O 2À , 84 OH À , 36 CAA À , six NO 3 À , 24 H 2 O, and twelve alcohol ligands as well as one NO 3 À and two Cl À mounted in the intra-cluster void through hydrogen bonding. To acquaint the structure and the assembly of complex 2 clearly, the barrel-like cluster can be devised into three layers, one middle {Gd 24 6 } section and two outer {Gd 18 12 ing a loop. It should be noted that the six central Gd III ions shared by the six {Gd 4 } units almost lie in the same plane with the six Gd III ions in the rim of the loop.…”

“…In the field of coordination and material chemistry, high-nuclearity clusters have attracted intense interest of scientists over recent years not only for their aesthetically pleasing structures and topologies but also because of their interesting properties. [1][2][3][4][5][6][7][8][9][10][11] Some types of large clusters, such as polyoxometalates, [2] metal chalcogenides, [3] inorganic fullerenelike molecules, [4] and oxo-clusters containing d-and/or fblock metals, [5-10, 12, 15-20] have been reported. Depending on the nanoscale size, shape, and composition of large clusters, they have found relevance in the areas of optics, electronics, magnetism, catalysts, and host-guest chemistry.…”

“…A burgeoning subclass within high-nuclearity clusters is the lanthanide hydroxide complex, [9,10,19,20] which exhibits promising magnetic properties originating from the 4f electronic configurations, for example, for single molecular magnets [11] or molecular magnetic coolers. [12a, 15-20] A successful strategy to synthesize high-nuclearity clusters is the employment of suitable ligands, such as carboxylates, [5,7] alcamines, [6] and polyketonates, [10] to control the growth of the metal cores to obtain clusters in finite size. Previous researches have also identified that the incorporation of small anions is an effective method to prepare large clusters.…”

“…6 A C H T U N G T R E N N U N G {CuII 5 Gd 4 } [17c] 31 (90) 61.7 A C H T U N G T R E N N U N G {Gd 2 }[19a] 41.6 (70)83.2 A C H T U N G T R E N N U N G {Gd 7 } [20b] 23 (70) 41.3 A C H T U N G T R E N N U N G {Gd 12 } [9e] 35H T U N G T R E N N U N G (OAc) 3 A C H T U N G T R E N N U N G (H 2 O) 0H T U N G T R E N N U N G (HCOO)A C H T U N G T R E N N U N G (C 8 H 4 O 4 )] n T U N G T R E N N U N G [Gd 6 (OH) 8 A C H T U N G T R E N N U N G (suc) 5 A C H T U N G T R E N N U N G (H 2 O) 2 ] n Ac = acetyl. [b] Suc = succinate.…”