A Unique Asymmetric [Mn] Triple-Stranded Helicate from a Symmetric Pentadentate Ligand

Abstract

Eine neuartige Topologie innerhalb der Familie der Metallohelicate fand sich mit dem Komplex [Mn3(HL)3] (die Struktur im Kristall ist gezeigt). Der neuartige fünfzähnige O‐Ligand, H3L, reagiert mit Mn(OAc)2 unter Bildung des dreisträngigen Helicats, das eine unerwartete asymmetrische Anordnung der Metallionen entlang der Molekülachse sowie intramolekulare magnetische Kopplung aufweist.

Ligand-Templated Four-Metal Chains Dimerize into a Unique [CuII8] Cluster

“…We have reported the synthesis of an O‐pentadentate donor possessing a phenol and two β ‐diketone units (H 3 L), which was conceived to direct the formation of chains of closely spaced transition metals 3. Initial efforts into the investigation of its coordination properties involved reactions with Mn II ions, and led to the preparation of a trinuclear complex with formula [Mn 3 (HL) 3 ] which displayed an asymmetric array of metals 4. A significant step forward in the exploration of the templating capability of this new ligand is reported here with the fascinating methoxide‐mediated aggregation of two ligand‐templated [Cu 4 ] chains into an entirely new octanuclear Cu II cluster held together by a fully deprotonated form of H 3 L. …”

Ligand-Templated Four-Metal Chains Dimerize into a Unique [CuII8] Cluster

“…

Within the context of what has been termed coordination supramolecular chemistry, remarkable progress has been made in the design and preparation of multidentate ligands capable of participating in complicated molecular structures upon complexation, in predetermined manners, with transition metals. [4] A significant step forward in the exploration of the templating capability of this new ligand is reported here with the fascinating methoxide-mediated aggregation of two ligand-templated [Cu 4 ] chains into an entirely new octanuclear Cu II cluster held together by a fully deprotonated form of H 3 L.The title compound was prepared by treating a methanolic solution of Cu(NO 3 ) 2 ¥ 3 H 2 O with a solution containing 0.125 equivalents of H 3 L and 1.8 equivalents of NtBu 4 OH in MeOH. Thus, in recent years, a few important reports have appeared describing the formation of new magnetic transition metal clusters through the template action of specifically designed multinucleating ligands.

…”

“…Thus, in recent years, a few important reports have appeared describing the formation of new magnetic transition metal clusters through the template action of specifically designed multinucleating ligands. [4] A significant step forward in the exploration of the templating capability of this new ligand is reported here with the fascinating methoxide-mediated aggregation of two ligand-templated [Cu 4 ] chains into an entirely new octanuclear Cu II cluster held together by a fully deprotonated form of H 3 L. [3] Initial efforts into the investigation of its coordination properties involved reactions with Mn II ions, and led to the preparation of a trinuclear complex with formula [Mn 3 (HL) 3 ] which displayed an asymmetric array of metals.…”