Selective Pathway toward Heteroleptic Spin-Crossover Iron(II) Complexes with Pyridine-Based N-Donor Ligands.

A new synthetic pathway is devised to selectively produce previously elusive heteroleptic iron(II) complexes of terpyridine and N,N'-disubstituted bis(pyrazol-3-yl)pyridines that stabilize the opposite spin states of the metal ion. Such a combination of the ligands in a series of the heteroleptic complexes induces the spin-crossover (SCO) not experienced by the homoleptic complexes of these ligands or shifts it to lower/higher temperatures respective to the SCO-active homoleptic complex. The midpoint temperatures of the resulting SCO span from ca. 200 K to the ambient temperature and beyond the highest temperature accessible by NMR spectroscopy and SQUID magnetometry. The proposed "one-pot" approach is applicable to other N-donor ligands to selectively produce heteroleptic complexes─including those inaccessible by alternative synthetic pathways─with highly tunable SCO behaviors for practical applications in sensing, switching, and multifunctional devices.

Unravelling of a [High Spin-Low Spin] ↔ [Low Spin-High Spin] Equilibrium in Spin-Crossover Iron(II) Dinuclear Helicates Using Paramagnetic NMR Spectroscopy.

Spin-crossover between high-spin (HS) and low-spin (LS) states of selected transition metal ions in polynuclear and polymeric compounds is behind their use as multistep switchable materials in breakthrough electronic and spintronic devices. We report the first successful attempt to observe the dynamics of a rarely found broken-symmetry spin state in binuclear complexes, which mixes the states [HS-LS] and [LS-HS] on a millisecond timescale. The slow exchange between these two states, which was identified by paramagnetic NMR spectroscopy in solutions of two spin-crossover iron(II) binuclear helicates that are amenable to molecular design, opens a path to double quantum dot cellular automata for information storage and processing.

Room-Temperature Spin Crossover in a Solution of Iron(II) Complexes with N,N'-Disubstituted Bis(pyrazol-3-yl)pyridines.

Here, we report a combined study of the effects of two chemical modifications to an N,N'-disubstituted bis(pyrazol-3-yl)pyridine (3-bpp) and of different solvents on the spin-crossover (SCO) behavior in otherwise high-spin iron(II) complexes by solution NMR spectroscopy. The observed stabilization of the low-spin state by electron-withdrawing substituents in the two positions of the ligand that induce opposite electronic effects in SCO-active iron(II) complexes of isomeric bis(pyrazol-1-yl)pyridines (1-bpp) was previously hidden by NH functionalities in 3-bpp precluding the molecular design of SCO compounds with this family of ligands. With the recent SCO-assisting substituent design, the uncovered trends converged toward the first iron(II) complex of N,N'-disubstituted 3-bpp to undergo an almost complete SCO centered at room temperature in a less polar solvent of a high hydrogen-bond acceptor ability.

Transport properties of nitrile and carbonate solutions of [P66614][NTf2] ionic liquid, its thermal degradation and non-isothermal kinetics of decomposition.

The electrical conductivity, density and diffusion coefficients of trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide ([P66614][NTf2]) ionic liquid and its binary solutions in acetonitrile, propionitrile, dimethyl and diethyl carbonates were measured in the temperature range of 293-348 K. The electrical conductivity - ionic liquid mole fraction dependencies for the binary solutions were fitted with the empirical Casteel-Amis equation. The temperature dependencies of electrical conductivity were analyzed using the Arrhenius, Litovitz and Vogel-Fulcher-Tammann approaches. The dependences of the Arrhenius activation energy and pre-exponential factor on the mole fraction of ionic liquid in the solutions were fitted with the empirical equations proposed in the literature. The thermo-gravimetric analysis combined with mass spectrometry demonstrated the high thermal stability of [P66614][NTf2] up to 600 K. At higher temperatures the decomposition of [P66614][NTf2] proceeded via the elimination of alkyl radicals as a result of the nucleophilic attack of reactive intermediates to the [P66614]+ cation with the formation of trialkylphosphines. The activation energies of the thermal destruction of [P66614][NTf2] were calculated using the Kissinger equation and non-linear integral isoconversional model.

Direct imidation of lactones via catalytic oxo/imido heterometathesis.

We report the first examples of direct imidation of lactones giving the corresponding cyclic imidates via oxo/imido heterometathesis with N-sulfinylamines catalysed by a well-defined silica-supported Ti imido complex.