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A switch in time: A fast precipitation technique was used to prepare 75 nm FeII spin-crossover nanocrystals. Their photoswitching dynamics, based on the light-induced excited spin-state trapping effect, has been investigated by means of optical spectroscopy. A significant variation of the switching proprieties is observed compared to similar but amorphous nanoparticles. |
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The photoreactivity of two iron(II)−styrylpyridine frameworks Fe(stpy)4(NCSe)2 (stpy = 4-styrylpyridine) has been investigated for the very first time in a crystalline solid. A quantitative cis-to-trans isomerization of stilbenoids is shown to occur in the confined environment of the inorganic solid. The photochromic reaction was driven by a visible excitation into the metal-to-ligand charge transfer absorption of the high-spin all-cis complex. The solid-state transformation is accompanied by a unit-cell volume increase and an amorphization. Interestingly, the photoproduct formed by irradiating the high-spin all-cis reactant undergoes a spin conversion when the temperature is decreased. This observation is related to the “ligand-driven light-induced spin change” effect in a constrained environment. |
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We report an in-depth theoretical study of 4-styrylpyridine in its singlet S0 ground state. The geometries and the relative stabilities of the trans and cis isomers were investigated within density functional theory (DFT) as well as within Hartree-Fock (HF), second-order Møller-Plesset (MP2), and coupled cluster (CC) theories. The DFT calculations were performed using the B3LYP and PBE functionals, with basis sets of different qualities, and gave results that are very consistent with each other. The molecular structure is thus predicted to be planar at the energy minimum, which is associated with the trans conformation, and to become markedly twisted at the minimum of higher energy, which is associated with the cis conformation. The results of the calculations performed with the post-HF methods approach those obtained with the DFT methods, provided that the level of treatment of the electronic correlation is high enough and that sufficiently flexible basis sets are used. Calculations carried out within DFT also allowed the determination of the geometry and the energy of the molecule at the biradicaloid transition state associated with the thermal cis ↔trans isomerization and at the transition states associated with the enantiomerization of the cis isomer and with the rotations of the pyridinyl and phenyl groups in the trans and cis isomers. Car-Parrinello molecular dynamics simulations were also performed at 50, 150, and 300 K using the PBE functional. The studies allowed us to evidence the highly flexible nature of the molecule in both conformations. In particular, the trans isomer was found to exist mainly in a nonplanar form at finite temperatures, while the rotation of the pyridinyl ring in the cis isomer was incidentally observed to take place within ≈1 ps during the simulation carried out at 150 K on this isomer. |
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The photophysical properties of the ferric catecholate spin-crossover compounds [(TPA)Fe(R-Cat)]X (TPA=tris(2-pyridylmethyl)amine; X=PF6-, BPh4-; R-Cat=catecholate dianion substituted by R=NO2, Cl, or H) are investigated in the solid state. The catecholate-to-iron(III) charge-transfer bands are sensitive both to the spin state of the metal ion and the charge-transfer interactions associated with the different catecholate substituents. Vibronic progressions are identified in the near-infrared (NIR) absorption of the low-spin species. Evidence for a low-temperature photoexcitation process is provided. The relaxation dynamics between 10 and 100 K indicate a pure tunneling process below ≈40 K, and a thermally activated region at higher temperatures. The relaxation rate constants in the tunneling regime at low temperature, kHL(T→0), vary in the range from 0.58 to 8.84 s-1. These values are in qualitative agreement with the inverse energy-gap law and with structural parameters. A comparison with ferrous spin-crossover complexes shows that the high-spin to low-spin relaxation is generally faster for ferric complexes, owing to the smaller bond length changes for the latter. However, in the present case the corresponding rate constants are smaller than expected based on the single configurational coordinate model. This is attributed to the combined influence of the electronic configuration and the molecular geometry. |