Hierarchical assembly of discrete copper(ii) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands

Abstract

The sequential interaction of preformed [Cu 2 (L 1 ) 2 (THF) 2 ] (where H 2 L 1 is 1,1-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione incorporating a 1,3-phenylene linker between its two β-diketone domains) and [Cu 2 (L 4 ) 2 ]·2H 2 O (where H 2 L 4 is 1,1-(4,4'-oxybiphenylene)-bis(4,4-dimethylpentane-1,3-dione) incorporating a flexible oxybiphenylene linkage between the two β-diketone groups) with the potentially difunctional aliphatic non-planar co-ligands, N-methylpiperazine (mpip), N,N'-dimethylpiperazine (dmpip) and 1,4-thiomorpholine (thiomorph) is reported. A series of extended molecular assemblies exhibiting a range of di-and tetranuclear assemblies were obtained and their X-ray structures determined.

Quantum coherence in a processable vanadyl complex: new tools for the search of molecular spin qubits

“…Even if the crucial aspect of qubits entanglement has not been addressed in this work it can be easily achieved through connection of β-diketonate pockets in more complex architectures. 58 , 59 This approach has already been successfully employed to couple different spin centers 60 and to address them individually in resonance experiments in particular in lanthanide polynuclear complexes thanks to their significantly different g -factors. 61 …”

Reversible Pressure‐Controlled Depolymerization of a Copper(II)‐Containing Coordination Polymer

“…The copper atoms bridged by a piperazine unit are separated by 6.7477(6) Å. The structure of 3 differs markedly from that of [{Cu 2 L 2 } 2 (1‐methylpiperazine) 2 ]⋅2(1‐methylpiperazine) (R= t Bu) ( 4 ) reported previously, which is a discrete dinuclear species with 5‐coordinate copper(II) centres to which axial 1‐methylpiperazine coligands are bound on opposite sides of the Cu 2 (L) 2 coordination plane via their secondary N‐donors (Figure S4); this product was synthesized employing different conditions from those used for 3 .…”

“…Cu II complexes [Cu 2 L 2 (solvent) n ], incorporating dinuclear “platforms” of type 1 , interact with a variety of heterocyclic nitrogen ligands to form both discrete and framework structures containing either 5‐ or 6‐coordinate copper ions . For example, recrystallization of previously reported [Cu 2 L 2 (THF) 2 ] (Cu 2 L 2 = 1 ; R= t Bu) from N ‐methylmorpholine resulted in the discrete binuclear complex, [Cu 2 L 2 ( N ‐methylmorpholine) 2 ] . We have investigated the effect of pressure on this product by X‐ray diffraction with the aid of a diamond anvil cell (DAC) .…”

A Zn(II) Metallocycle as Platform to Assemble a 1D + 1D → 1D Polyrotaxane via π···π Stacking of an Ancillary Ligand

“…Lu et al [8] reported the first example of a 2D poly-pseudo-rotaxane developed starting from a discrete stool-like metallocycle. Metallorings, based on transition metals capable of expanding their coordination, can be used as platforms to hierarchically assemble extended metallo-supramolecular systems [12][13][14][15] as demonstrated by Lindoy et al This strategy has also allowed to isolate a 1D polyrotaxane, where a copper-based metallocycle and a pyridyl bridging ligand self-assemble to form a 1D coordination polymer (the axle) and a discrete rectangular box (the stopper) [10].…”

“…pyridyl bridging ligand self-assemble to form a 1D coordination polymer (the axle) and a discrete rectangular box (the stopper) [10]. In order to design metallocycles bearing metal ions that can change their coordination sphere by ligand substitution or by expanding the coordination number, 2+ charged metal ions and bis-βdiketone ligands have been proven to be ideal building blocks [12][13][14][15]. For instance, we have previously demonstrated that Cu(II) and a bis-β-diketone can be used to self-assemble a constitutional dynamic library of metallocycles [16], where the interactions with σ-donor guests via Cu-N bonds drive the system toward a triangular metallobox [17,18] that can be used also to catalyze host reactions [19].…”