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Abstract Cooperativity among spin centres has long been the royal road in spin crossover (SCO) research to impose magnetic bistability in terms of thermal hysteresis. In this work we access magnetic multi-inert states of the iron(III) compound {FeL2[B(Ph)4]} ≡ FeB at low temperature, in addition to thermal bistability. The packing of the low-spin and high-spin forms of crystalline FeB differs only marginally what ultimately leads to structural conservatism. This indicates that the SCO-immanent breathing of the complex cation is almost fully compensated by the anion matrix. The unique cooling rate dependence of the residual low-temperature magnetisation in FeB unveils continuous switching between the trapped high-spin (ON) and the relaxed low-spin state (OFF). The macroscopic ratio of the spin states (ON:OFF) can be adjusted as a simple function of the cooling rate. That is, cooperative spin crossover can be the source of bistable and multi-inert system states in the very same material.

A new family of photochromic diarylethene-based ligands bearing a 2-(imidazol-2-yl)pyridine coordination unit has been developed. Four members of the new family have been synthesized. The photoactive ligands feature non-aromatic ethene bridges (cyclopentene, cyclopentenone, and cyclohexenone), as well as closely spaced photoactive and metal coordination sites aiming a strong impact of photocyclization on the electronic structure of the coordinated metal ion. The ligands with cyclopentenone and cyclohexenone bridges show good cycloreversion quantum yields of 0.20–0.32. The thermal stability of closed-ring isomers reveals half-lives of up to 20 days in solution at room temperature. The ligands were used to explore coordination chemistry with iron(II) targeting photoswitchable spin-crossover complexes. Unexpectedly, dinuclear and tetranuclear iron(II) complexes were obtained, which were thoroughly characterized by X-ray crystallography, magnetic measurements, and Mössbauer spectroscopy. The formation of multinuclear complexes is facilitated by two coordination sites of the diarylethene, acting as a bridging ligand. The bridging nature of the diarylethene in the complexes prevents photocyclization.

The synthesis of chelating N-heterocyclic carbene (NHC) complexes with considerable π-acceptor properties can be a challenging task. This is due to the dimerization of free carbene ligands, the moisture sensitivity of reaction intermediates or reagents, and challenges associated with the workup procedure. Herein, we report a general route using transmetalation from magnesium−NHCs. Notably, this route gives access to transition-metal complexes in quantitative conversion without the formation of byproducts. It therefore produces transition-metal complexes outperforming the conventional routes based on free or lithium-coordinated carbene, silver complexes, or in situ metalation in dimethyl sulfoxide (DMSO). We therefore propose transmetalation from magnesium−NHCs as a convenient and general route to obtain NHC complexes.

(S,S)-Ethylenediamine-N,N’-di-2-propanoic acid hydrochloride, (S,S)-H2eddp·HCl, was prepared and its crystal structure determined. The compound was characterized by infrared and 1H- and 13C-NMR spectroscopy. It forms P1 in the space group of a triclinic crystal system with a = 5.3902(2) Å, b = 5.8967(2) Å, c = 10.3319(2) Å, a = 99.625(2)°, b = 91.645(2)°, g = 109.995(2)° and Z = 1.

In the title compound, alternatively called α-hydroxy-γ-alkylidenebutenolide, C12H16O3, two independent molecules (A and B) crystallize in the asymmetric unit in each of which the 5,6-dihydrobenzo ring has an envelope conformation. The torsion angle along the butadiene chain in the γ-alkylidenebutenolide core is −177.9 (2)° for molecule A and 179.9 (2)° for molecule B. In the crystal, O—H...O hydrogen bonds between hydroxyl and carbonyl groups of adjacent independent molecules form dimers with R22(10) loops.