Complexes of a novel multinucleating poly-β-diketonate ligand

A Zig‐Zag [MnII4] Cluster from a Novel Bis(β‐diketonate) Ligand

“…Reactions of the latter with M(OAc) 2 salts have resulted invariably in the formation of complexes of the type [M 2 (H 2 L2) 2 (S) n ] (n = 2 or 4; S = solvent; M = Mn, Ni, Co, Cu). [16] Similar dinuclear compounds have been obtained with H 3 L1. [18] However, in the absence of a coordinating solvent, molecules exhibiting higher occupancy, [Co 3 (HL1) 3 ] and [Mn 3 (HL1) 3 ], were characterized, which represented a new asymmetric topology within the context of coordination helicates.…”

“…Of these molecular species, only a minority have the metal ions disposed in close proximity so as to show cooperative effects resulting from strong magnetic-exchange interactions [13] or metalmetal bonding. [14] We have been interested in preparing new ligands incorporating various β-diketone units and other donor groups in a linear fashion (H 3 L1 and H 4 L2 in [ Scheme 1), [15,16] aimed at forming molecular strings of metal ions in close proximity. Maximum occupancy of their coordination pockets would result in tetranuclear clusters in form of [M 4 ] chains [17] for H 3 L1 and aligned [M 2 ] 2 dimers of dimers for H 4 L2.…”

“…[ Scheme 1), [15,16] aimed at forming molecular strings of metal ions in close proximity. Maximum occupancy of their coordination pockets would result in tetranuclear clusters in form of [M 4 ] chains [17] for H 3 L1 and aligned [M 2 ] 2 dimers of dimers for H 4 L2.…”

“…This second course of action has led to the production of a large amount of polynuclear edifices displaying sophisticated shapes and architectures, such as helicates, [9] grids, [10] cylinders, [11] catenates, [12] and many more. Of these molecular species, only a minority have the metal ions disposed in close proximity so as to show cooperative effects resulting from strong magnetic-exchange interactions [13] or metalmetal bonding.[ Scheme 1), [15,16] aimed at forming molecular strings of metal ions in close proximity. Maximum occupancy of their coordination pockets would result in tetranuclear clusters in form of [M 4 ] chains [17] for H 3 L1 and aligned [M 2 ] 2 dimers of dimers for H 4 L2.…”

Designed Topology and Site‐Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes

“…[27] Recently, we have demonstrated that adding the necessary amount of a stronger base (NBu 4 OH) to an NiA C H T U N G T R E N N U N G (ClO 4 ) 2 /H 4 L reaction mixture (in the 2:1 molar ratio) causes complete deprotonation of the ligand and formation of the complex [Ni 4 L 2 (py) 6 ] (1; py= pyridine), [17] which exhibits the topology expected for a full metal load (Scheme 1, bottom). A striking feature of complex 1 is the fact that the external metals of the chain exhibit five-coordination, which is rather unusual for Ni II , whereas the internal Ni centres are in the preferred octahedral geometry.…”