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We use femtosecond optical pump-probe spectroscopy to study the Light Induced Excited Spin State Trapping (LIESST) dynamics in an FeII spin-crossover material. In these systems, LIESST derives from fast molecular switching induced by light from low (LS, S = 0) to high spin (HS, S = 2) states, as reported for molecules in solution as well as in the solid state. Since the direct LS-to-HS conversion is forbidden by selection rules, the switching dynamics involves intermediate electronic states such as metal-to-ligand charge transfer (MLCT) or ligand-field excited states of singlet or triplet nature. In addition, the HS state is structurally trapped by the elongation of the metal-ligand bond, which is accompanied by the coherent activation and damping of the molecular breathing mode. The ultrafast LIESST dynamics was mainly investigated in FeN6 ligand field systems with almost octahedral symmetry, under MLCT excitation. Our recent study on the FeII(pap-5NO2)2 spin-crossover material, with a FeIIN4O2 ligand field of C2 symmetry, has shown that in addition to MLCT bands, optical excitation, through quite intense and low-energy shifted d-d bands, can also drive LIESST. Compared to MLCT, d-d excitation involves shorter-lived intermediates, drives faster LS-to-HS switching, and enhances the coherent structural dynamics. In this paper, we present an ultrafast study of the pump wavelength dependence of LIESST and we evidence a photoselective crossover from the MLCT to the d-d pathways. [ABSTRACT FROM AUTHOR]

We investigated the effect of an externally applied pressure on the iron(iii) Schiff-base compound [Fe(3-OMeSalEen)2]PF6 (H-3-OMeSalEen, condensation product of 3-methoxy-substituted salicylaldehyde and N-ethylethylenediamine), which at ambient pressure displays a thermal spin transition with a 3 K wide hysteresis loop centered at 164 K. Raman spectrometry revealed the occurrence of a complete spin-state switching process for a pressure of P1/2 = 8–9 kbar at room temperature. The evolution of lattice parameters as a function of pressure was followed by X-ray diffraction measurements on single crystals, highlighting the important microscopic aspects at the origin of the pressure-induced transition, i.e. an anisotropic response and a high compressibility of the HS molecular lattice. Variable temperature magnetic susceptibility measurements at different applied pressures revealed the smoothening of the spin transition curves and a linear increase of the transition temperatures by ca. 16.4 (1.0) K kbar−1, in good agreement with the Clausius–Clapeyron law. The non-negligible influence of the pressure transmitting oils on the intrinsic transition properties was also evidenced and attributed to mechanical interactions between the particles and the solidified matrix. [ABSTRACT FROM AUTHOR]

We report on the size reduction of the neutral Fe(phen)2(NCS)2 prototypical compound exhibiting a cooperative spin-crossover associated with a first-order phase transition (at ca. 176 K). We use the [Fe(phen)3](NCS)2 ionic precursor and the solvent-assisted precipitation technique to prepare an array of crystalline objects with sizes varying over two orders of magnitude (from 15 up to 1400 nm). TEM, X-ray diffraction and IR measurements provide evidences for the formation of particles of neutral and ionic species, which results from the interplay between the relevant chemical equilibrium and the reaction kinetics (ligand extraction, complex precipitation), and the modulation of the latter by physico-chemical parameters. A thermal transformation of diamagnetic nanocrystals of [Fe(phen)3](NCS)2 leads to spin-crossover particles of Fe(phen)2(NCS)2 of a comparable size. Powders of nano-, micro- and polycrystals of Fe(phen)2(NCS)2 present X-ray diffractograms typical of the so-called polymorph II. The importance of size effects on the cooperative spin-crossover process was probed with magnetic, Mössbauer, Raman and IR spectroscopic measurements. Each sample exhibits spin-state switching of the Fe(ii) ions. The salient features are: a cooperativity preserved at the micrometric scale, a very limited downshift of the transition temperature and an asymmetric spreading of the thermal process (over ca. 100 K) with the size reduction. At temperatures close to room temperature, the process appears to be quasi complete whatever the size of the samples. This result, extracted from Raman data, was confirmed by Mössbauer measurements in the case of the largest objects (LS residue ＜5–10% for bulk and microparticles). Below 150 K, a very efficient low-spin to high-spin photoexcitation was induced by the Raman laser beam in all the samples which prevents the extraction of the high-spin fraction in this temperature range. However variable temperature IR spectra of the 29 nm particles indicate that the HS residue, that is close to zero in the case of microparticles, does not drastically increase (＜30%) for the smallest particles. The processing of a number of related spin-crossover compounds in the form of nanoparticles may be achieved with this general approach. [ABSTRACT FROM AUTHOR]

The spin-crossover compound [(TPA)Fe(TCC)]PF6 was experimentally investigated using time-resolved optical pump and supercontinuum probe technique. Changes of VIS optical density at thermal equilibrium of a crystal with different high-spin/low-spin fractions are compared to changes recorded picoseconds after femtosecond laser excitation. A white light snapshot of the high-spin state at 180 K is extracted from time-resolved spectra. Our results indicate that the temperature of the electronic state affects the absorption spectra of high- and low-spin states. [ABSTRACT FROM AUTHOR]

We present the first time-resolved pump-probe experiment performed at synchrotron SOLEIL at the CRISTAL diffraction beamline. The time-resolved setup will be used in the near future for sub-ns time resolution experiments. We studied spin state switching in a [TPA Fe(III) TCC] PF6 single crystal as induced by a ≈ 6 ns laser pulse (1064 nm), by measuring the 3D diffraction volume of the 002 Bragg reflection as a function of time after excitation. The intensity profiles (rocking curves) are found to evolve at two characteristic timescales, namely hundreds of ns and few μs, exhibiting subtle profile changes and peak broadenings. Consistently with previous studies, we interpret these features as due to structural inhomogeneities related to laser-induced deformation wave propagation and heat diffusion, which both start from the absorbing sites. [ABSTRACT FROM AUTHOR]

We present the first time-resolved pump-probe experiment performed at synchrotron SOLEIL at the CRISTAL diffraction beamline. The time-resolved setup will be used in the near future for sub-ns time resolution experiments. We studied spin state switching in a [TPA Fe(III) TCC] PF6 single crystal as induced by a ≈ 6 ns laser pulse (1064 nm), by measuring the 3D diffraction volume of the 002 Bragg reflection as a function of time after excitation. The intensity profiles (rocking curves) are found to evolve at two characteristic timescales, namely hundreds of ns and few μs, exhibiting subtle profile changes and peak broadenings. Consistently with previous studies, we interpret these features as due to structural inhomogeneities related to laser-induced deformation wave propagation and heat diffusion, which both start from the absorbing sites. [ABSTRACT FROM AUTHOR]

Competing Interests: We are all employees of The Lancet Group and members of The Lancet Research Integrity Group. MC is a Council member of the Committee on Publication Ethics (COPE), and has received travel support from COPE for Council meetings, from the World Conference on Research Integrity (WCRI) as a speaker, and from the Nuffield Department of Primary Care Health Sciences, University of Oxford as a workshop presenter. ALS has an unpaid affiliation with Stellenbosch University as Extraordinary Associate Professor in Paediatrics and Child Health. JB has an unpaid affiliation with the University of North Carolina as an Adjunct Professor. We declare no other competing interests.

During natural behavior, an action often needs to be suddenly stopped in response to an unexpected sensory input-referred to as reactive stopping. Reactive stopping has been mostly investigated in humans, which led to hypotheses about the involvement of different brain structures, in particular the hyperdirect pathway. Here, we directly investigate the contribution and interaction of two key regions of the hyperdirect pathway, the orbitofrontal cortex (OFC) and subthalamic nucleus (STN), using dual-area, multielectrode recordings in male rats performing a stop-signal task. In this task, rats have to initiate movement to a go-signal, and occasionally stop their movement to the go-signal side after a stop-signal, presented at various stop-signal delays. Both the OFC and STN show near-simultaneous field potential reductions in the beta frequency range (12-30 Hz) compared with the period preceding the go-signal and the movement period. These transient reductions (∼200 ms) only happen during reactive stopping, which is when the stop-signal was received after action initiation, and are well timed after stop-signal onset and before the estimated time of stopping. Phase synchronization analysis also showed a transient attenuation of synchronization between the OFC and STN in the beta range during reactive stopping. The present results provide the first direct quantification of local neural oscillatory activity in the OFC and STN and interareal synchronization specifically timed during reactive stopping., Competing Interests: The authors declare no competing financial interests., (Copyright © 2024 the authors.)

The orbitofrontal cortex and amygdala collaborate in outcome-guided decision-making through reciprocal projections. While serotonin transporter knockout (SERT-/-) rodents show changes in outcome-guided decision-making, and in orbitofrontal cortex and amygdala neuronal activity, it remains unclear whether SERT genotype modulates orbitofrontal cortex-amygdala synchronization. We trained SERT-/- and SERT+/+ male rats to execute a task requiring to discriminate between two auditory stimuli, one predictive of a reward (CS+) and the other not (CS-), by responding through nose pokes in opposite-side ports. Overall, task acquisition was not influenced by genotype. Next, we simultaneously recorded local field potentials in the orbitofrontal cortex and amygdala of both hemispheres while the rats performed the task. Behaviorally, SERT-/- rats showed a nonsignificant trend for more accurate responses to the CS-. Electrophysiologically, orbitofrontal cortex-amygdala synchronization in the beta and gamma frequency bands during response selection was significantly reduced and associated with decreased hubness and clustering coefficient in both regions in SERT-/- rats compared to SERT+/+ rats. Conversely, theta synchronization at the time of behavioral response in the port associated with reward was similar in both genotypes. Together, our findings reveal the modulation by SERT genotype of the orbitofrontal cortex-amygdala functional connectivity during an auditory discrimination task., (© The Author(s) 2024. Published by Oxford University Press.)