Bistable compounds that exist in two interchangeable phases under identical conditions can act as switches under external stimuli. Among such switchable materials, coordination complexes have energy levels (or phases) that are determined by the electronic states of their constituent metal ions and ligands. They can exhibit multiple bistabilities and hold promise in the search for multifaceted materials that display different properties in different phases, accessible through the application of contrasting external stimuli. Molecular systems that exhibit both thermo- and photoinduced magnetic bistabilities are excellent candidates for such systems. Here we describe a cyanide-bridged [CoFe] one-dimensional chiral coordination polymer that displays both magnetic and electric bistabilities in the same temperature range. Both the electric and magnetic switching probably arise from the same electron-transfer coupled spin-transition phenomenon, which enables the reversible conversion between an insulating diamagnetic phase and either a semiconducting paramagnetic (thermoinduced) or a type of ferromagnetic single-chain magnet (photoinduced) state.

The reactions of [γ-SiW10O36]8– represent one of the most important synthetic gateways into a vast array of polyoxotungstate chemistry. Herein, we set about exploring the transformation of the lacunary polyoxoanion [β2-SiW11O39]8– into [γ-SiW10O36]8– using high-resolution electrospray mass spectrometry, density functional theory, and molecular dynamics. We show that the reaction proceeds through an unexpected {SiW9} precursor capable of undertaking a direct β → γ isomerization via a rotational transformation. The remarkably low-energy transition state of this transformation could be identified through theoretical calculations. Moreover, we explore the significant role of the countercations for the first time in such studies. This combination of experimental and the theoretical studies can now be used to understand the complex chemical transformations of oxoanions, leading to the design of reactivity by structural control.

The cyanide-bridged [CoFe] one-dimensional chain, [Co(II)((R)-pabn)][Fe(III)(Tp)(CN)3](BF4)·MeOH·2H2O, where (R)-pabn = (R)-N2,N(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) (S = 1/2) and high spin Co(II) (S = 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) t2g 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.

A bulky bidentate ligand was used to stabilize a macrocyclic [Fe(III)8Co(II)6] cluster. Tuning the basicity of the ligand by derivatization with one or two methoxy groups led to the isolation of a homologous [Fe(III)8Co(II)6] species and a [Fe(III)6Fe(II)2Co(III)2Co(II)2] complex, respectively. Lowering the reaction temperatures allowed isolation of [Fe(III)6Fe(II)2Co(III)2Co(II)2] clusters with all three ligands. Temperature-dependent absorption data and corresponding experiments with iron/nickel systems indicated that the iron/cobalt self-assembly process was directed by the occurrence of solution-state electron-transfer-coupled spin transition (ETCST) and its influence on reaction intermediate lability.

Two decanuclear cyanide-bridged cage compounds were synthesized through the combination of chiral bidentate ligand-capped transition metal building blocks with hexacyanometalate ions, and their structural and magnetic properties were investigated.