Chiral Single-Chain Magnet: Helically Stacked [Mn^III₂Cu^II] Triangles

The one-dimensional complex [Mn^III₂Cu^II(μ₃-O)­(Cl-sao)₃(EtOH)₂]·EtOH (Mn₂Cu) was obtained by the metal replacement reaction of the trinuclear manganese complex (Et₃NH)­[Mn^III₃(μ₃-O)­Cl₂(Cl-sao)₃(MeOH)₂(H₂O)₂] with [Cu­(acac)₂]. The Mn₂Cu chain exhibits single-chain-magnet behavior with finite-size effects due to its large magnetic anisotropy

Multiredox Active [3 × 3] Copper Grids

A nonanuclear copper grid complex, [Cu^II₉(L)₆]­(BF₄)₆·1-PrOH·5H₂O (<b>1</b>·1-PrOH·5H₂O; L = 2,6-bis­[5-(2-pyridinyl)-1<i>H</i>-pyrazol-3-yl]­pyridine), was synthesized with a [3 × 3] grid structure consisting of nine Cu^II ions and six deprotonated ligands and displayed four-step quasi-reversible redox behavior from [Cu^II₉] to [Cu^I₄Cu^II₅]. The corresponding heterovalent complex [Cu^I₂Cu^II₇(L)₆]­(PF₆)₄·3H₂O (<b>2</b>·3H₂O) was successfully isolated and had a distorted core structure that radically changed the intramolecular magnetic coupling pathways

X‑ray Magnetic Circular Dichroism Investigation of the Electron Transfer Phenomena Responsible for Magnetic Switching in a Cyanide-Bridged [CoFe] Chain

The cyanide-bridged [CoFe] one-dimensional chain, [Co^II((<i>R</i>)-pabn)]­[Fe^III(Tp)­(CN)₃]­(BF₄)·MeOH·2H₂O, where (<i>R</i>)-pabn = (<i>R</i>)-<i>N</i>2,<i>N</i>(2′)-bis­(pyridin-2-ylmethyl)-1,1′-binaphthyl-2,2′-diamine and Tp = hydrotris­(pyrazolyl)­borate, exhibits magnetic and electric bistabilities originating from an electron transfer coupled spin transition between Fe–CN–Co pairs. The use of L-edge X-ray absorption spectroscopy (XAS) in combination with L-edge X-ray magnetic circular dichroism (XMCD) is explored for the investigation of the electronic structure and magnetization of Co and Fe ions separately, in both diamagnetic and paramagnetic states. It has been established from susceptibility results that the switching between diamagnetic and paramagnetic phases emanates from electron transfer between low spin Fe­(II) and Co­(III), resulting in low spin Fe­(III) (<i>S</i> = 1/2) and high spin Co­(II) (<i>S</i> = 3/2). The XAS and XMCD results are consistent with the bulk susceptibility measurements, where greater detail regarding the charge transfer process is determined. The Fe–CN–Co electron transfer pathway is highlighted by a strongly XMCD dependent transition to a cyanide back bonding orbital, giving evidence for strong hybridization with Fe­(III) t_2g orbitals. In addition to thermally induced and photoinduced switching, [CoFe] is found to exhibit a switching by grinding induced dehydration. Analysis of XAS shows that on grinding diamagnetic [CoFe], 75% of metal ions lock into the magnetic Co­(II)­Fe­(III) phase. Density functional theory calculations based on the [CoFe] crystal structure in the magnetic and nonmagnetic phases aid the spectroscopic results and provide a complementary insight into the electronic configuration of the [CoFe] 3d shells, quantifying the change in ligand field around Co and Fe centers on charge transfer