From Ultrafast Photoinduced Small Polarons to Cooperative and Macroscopic Charge-Transfer Phase Transition.

We study by femtosecond infrared spectroscopy the ultrafast and persistent photoinduced phase transition of the Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98∙0.2H2O material, induced at room temperature by a single laser shot. This system exhibits a charge-transfer based phase transition with a 75 K wide thermal hysteresis, centred at room temperature, from the low temperature Mn3+-N-C-Fe2+ tetragonal phase to the high temperature Mn2+-N-C-Fe3+ cubic phase. At room temperature, the photoinduced phase transition is persistent. However, the out-of-equilibrium dynamics leading to this phase is multi-scale. Femtosecond infrared spectroscopy, particularly sensitive to local reorganizations through the evolution of the frequency of the N-C vibration modes with the different characteristic electronic states, reveals that at low laser fluence and on short time scale, the photoexcitation of the Mn3+-N-C-Fe2+ phase creates small charge-transfer polarons [Mn2+-N-C-Fe3+]* within ≃ 250 fs. The local trapping of photoinduced intermetallic charge-transfer is characterized by the appearance of a polaronic infrared band, due to the surrounding Mn2+-N-C-Fe2+ species. Above a threshold fluence, when a critical fraction of small CT-polarons is reached, the macroscopic phase transition to the persistent Mn2+-N-C-Fe3+ cubic phase occurs within ≃ 100 ps. This non-linear photo-response results from elastic cooperativity, intrinsic to a switchable lattice and reminiscent of a feedback mechanism.

Domain Wall Dynamics in a Ferroelastic Spin Crossover Complex with Giant Magnetoelectric Coupling.

Pinned and mobile ferroelastic domain walls are detected in response to mechanical stress in a Mn3+ complex with two-step thermal switching between the spin triplet and spin quintet forms. Single-crystal X-ray diffraction and resonant ultrasound spectroscopy on [MnIII(3,5-diCl-sal2(323))]BPh4 reveal three distinct symmetry-breaking phase transitions in the polar space group series Cc → Pc → P1 → P1(1/2). The transition mechanisms involve coupling between structural and spin state order parameters, and the three transitions are Landau tricritical, first order, and first order, respectively. The two first-order phase transitions also show changes in magnetic properties and spin state ordering in the Jahn-Teller-active Mn3+ complex. On the basis of the change in symmetry from that of the parent structure, Cc, the triclinic phases are also ferroelastic, which has been confirmed by resonant ultrasound spectroscopy. Measurements of magnetoelectric coupling revealed significant changes in electric polarization at both the Pc → P1 and P1 → P1(1/2) transitions, with opposite signs. All these phases are polar, while P1 is also chiral. Remanent electric polarization was detected when applying a pulsed magnetic field of 60 T in the P1→ P1(1/2) region of bistability at 90 K. Thus, we showcase here a rare example of multifunctionality in a spin crossover material where the strain and polarization tensors and structural and spin state order parameters are strongly coupled.

Impact of the terahertz and optical pump penetration depths on generated strain waves temporal profiles in a V2O3 thin film.

Triggering new stable macroscopic orders in materials by ultrafast optical or terahertz pump pulses is a difficult challenge, complicated by the interplay between multiscale microscopic mechanisms, and macroscopic excitation profiles in samples. In particular, the differences between the two types of excitations are still unclear. In this article, we compare the optical response on acoustic timescale of a V2O3 Paramagnetic Metallic (PM) thin film excited by a terahertz (THz) pump or an optical pump, at room temperature. We show that the penetration depth of the deposited energy has a strong influence on the shape of the optical transmission signal, consistent with the modulation of permittivity by the superposition of depth-dependent static strain, and dynamical strain waves travelling back and forth in the sample layer. In particular, the temporal modulation of the optical transmission directly reflects the excitation profile as a function of depth, as well as the sign of the acoustic reflection coefficient between the film and the substrate. The acoustic mismatch between the V2O3 layer and the substrate was also measured. The raw data were interpreted with a one-dimensional analytical model, using three fitting parameters only. These results are discussed in the context of triggering phase transitions by ultrafast pump pulses. To the best of our knowledge, this is the first report of the modulation of the optical transmission of V2O3 with a THz pump within the acoustic timescale.

Thermal and Magnetic Field Switching in a Two-Step Hysteretic MnIII Spin Crossover Compound Coupled to Symmetry Breakings.

A MnIII spin crossover complex with atypical two-step hysteretic thermal switching at 74 K and 84 K shows rich structural-magnetic interplay and magnetic-field-induced spin state switching below 14 T with an onset below 5 T. The spin states, structures, and the nature of the phase transitions are elucidated via X-ray and magnetization measurements. An unusual intermediate phase containing four individual sites, where 1 / 4 are in a pure low spin state, is observed. The splitting of equivalent sites in the high temperature phase into four inequivalent sites is due to a structural reorganization involving a primary and a secondary symmetry-breaking order parameter that induces a crystal system change from orthorhombic→monoclinic and a cell doubling. Further cooling leads to a reconstructive phase transition and a monoclinic low-temperature phase with two inequivalent low-spin sites. The coupling between the order parameters is identified in the framework of Landau theory.

Giant Magnetoelectric Coupling and Magnetic-Field-Induced Permanent Switching in a Spin Crossover Mn(III) Complex.

We investigate giant magnetoelectric coupling at a Mn3+ spin crossover in [MnIIIL]BPh4 (L = (3,5-diBr-sal)2323) with a field-induced permanent switching of the structural, electric, and magnetic properties. An applied magnetic field induces a first-order phase transition from a high spin/low spin (HS-LS) ordered phase to a HS-only phase at 87.5 K that remains after the field is removed. We observe this unusual effect for DC magnetic fields as low as 8.7 T. The spin-state switching driven by the magnetic field in the bistable molecular material is accompanied by a change in electric polarization amplitude and direction due to a symmetry-breaking phase transition between polar space groups. The magnetoelectric coupling occurs due to a γη2 coupling between the order parameter γ related to the spin-state bistability and the symmetry-breaking order parameter η responsible for the change of symmetry between polar structural phases. We also observe conductivity occurring during the spin crossover and evaluate the possibility that it results from conducting phase boundaries. We perform ab initio calculations to understand the origin of the electric polarization change as well as the conductivity during the spin crossover. Thus, we demonstrate a giant magnetoelectric effect with a field-induced electric polarization change that is 1/10 of the record for any material.

Exploring Ultrafast Photoswitching Pathways in RbMnFe Prussian Blue Analogue.

We study by femtosecond optical pump-probe spectroscopy the photoinduced charge transfer (CT) in the RbMnFe Prussian blue analogue. Previous studies evidenced the local nature of the photoinduced MnIII FeII → MnII FeIII process, occurring within less than 1 ps. Here we show experimentally that two photoswitching pathways exist, depending on the excitation pump wavelength, which is confirmed by band structure calculations. Photoexcitation of α spins corresponds to the Mn(d-d) band, which drives reverse Jahn-Teller distortion through the population of antibonding Mn-N orbitals, and induces CT within ≈190 fs. The process launches coherent lattice torsion during the self-trapping of the CT small-polaron. Photoexcitation of ß spins drives intervalence Fe→Mn CT towards non-bonding states and results in a slower dynamic.

Hysteresis Photomodulation via Single-Crystal-to-Single-Crystal Isomerization of a Photochromic Chain of Dysprosium Single-Molecule Magnets.

A one-dimensional coordination solid 1c is synthesized by reaction of a bispyridyl dithienylethene (DTE) photochromic unit with the highly anisotropic dysprosium-based single-molecule magnet [Dy(Tppy)F(pyridine)2]PF6. Slow magnetic relaxation characteristics are retained in the chain compound 1c, and photoisomerization of the bridging DTE ligand induces a single-crystal-to-single-crystal transformation that can be monitored using photocrystallography. Notably, the resulting chain compound 1o exhibits faster low-temperature relaxation than that of 1c, which is apparent in magnetic hysteresis data collected for both compounds as high as 4 K. Ab initio calculations suggest that this photomodulation of the magnetic relaxation behavior is due to crystal packing changes rather than changes to the crystal field splitting upon ligand isomerization.

Photoswitchable 11 nm CsCoFe Prussian Blue Analogue Nanocrystals with High Relaxation Temperature.

Photoswitchable 11 nm nanocrystals with the coordination network Cs{Co[Fe(CN)6]} were obtained using a template-free method. The nanocrystals were recovered from the colloidal solutions as solid materials surrounded by cetyltrimethylammonium (CTA) cations or embedded in the organic polymer polyvinylpyrrolidone (PVP). Complementary magnetic, spectroscopic, and structural techniques, including EPR spectroscopy, reveal a majority (∼70%) of the low-spin and photoactive diamagnetic CoIIIFeII pairs located in the core of the nanocrystals and a mixture of CoIIFeII and CoIIFeIII species present mainly within the shell of the objects. While bulk compounds with similar vacancy concentration do not exhibit noticeable photoinduced charge transfer, the observed photoactivity of the nanocrystals is ascribed to their nanometric size. The relaxation temperature of the photoinduced state shifts upward by ∼55 K when PVP is replaced by CTA. This is ascribed to the larger rigidity of the dense CsCoFe_CTA material, whose metastable state is lower than that for CsCoFe_PVP, leading to a larger relaxation energy barrier and, therefore, to a higher relaxation temperature.

Stress-Induced Domain Wall Motion in a Ferroelastic Mn3+ Spin Crossover Complex.

Domain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single-crystal X-ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry-breaking phase transitions in the mononuclear Mn3+ compound [Mn(3,5-diBr-sal2 (323))]BPh4 , 1. The first at 250 K, involves the space group change Cc→Pc and is thermodynamically continuous, while the second, Pc→P1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress-induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc-P1 transition.

Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods.

We review the tremendous advances in ultrafast X-ray science, over the past 15 years, making the best use of new ultrashort X-ray sources including table-top or large-scale facilities. Different complementary X-ray-based techniques, including spectroscopy, scattering, and diffraction, are presented. The broad and expanding spectrum of these techniques in the ultrafast time domain is delivering new insight into the dynamics of molecular systems, of solutions, of solids, and of biosystems. Probing the time evolution of the electronic and structural degrees of freedom of these systems on the time scales of femtosecond to picoseconds delivers new insight into our understanding of dynamical matter.

Temperature dependence of the cooperative out-of-equilibrium elastic switching in a spin-crossover material.

We present a study of a molecular material, [Feiii(3-MeO-SalEen)2]PF6, undergoing cooperative reversible photo-induced transition between low-spin state and high-spin state. By using temporally multiscale pump-probe laser spectroscopy, we explore the key parameters that influence the low-spin to high-spin conversion efficiency through long range elastic intermolecular interactions during the so-called elastic step, where crystalline volume expansion takes place. We rationalize our findings using Monte Carlo simulations, and a mechano-elastic model. The experimental results and the simulations support the existence of a fast mechanism by which molecules cooperatively switch through coupling to the lattice strain. The efficiency of the coupling process is shown to depend on several parameters including the initial thermal population and the instantaneous photo-induced population among others. Far below the crossover temperature, the elastic self-amplification occurs above a threshold photo-excitation. On approaching the thermal crossover, the threshold disappears and the photo-elastic conversion increases.

The First Observation of Hidden Hysteresis in an Iron(III) Spin-Crossover Complex.

Molecular magnetic switches are expected to form the functional components of future nanodevices. Herein we combine detailed (photo-) crystallography and magnetic studies to reveal the unusual switching properties of an iron(III) complex, between low (LS) and high (HS) spin states. On cooling, it exhibits a partial thermal conversion associated with a reconstructive phase transition from a [HS-HS] to a [LS-HS] phase with a hysteresis of 25 K. Photoexcitation at low temperature allows access to a [LS-LS] phase, never observed at thermal equilibrium. As well as reporting the first iron(III) spin crossover complex to exhibit reverse-LIESST (light-induced excited spin state trapping), we also reveal a hidden hysteresis of 30 K between the hidden [LS-LS] and [HS-LS] phases. Moreover, we demonstrate that FeIII spin-crossover (SCO) complexes can be just as effective as FeII systems, and with the advantage of being air-stable, they are ideally suited for use in molecular electronics.

Disentangling Ultrafast Electronic and Structural Dynamics with X-Ray Lasers.

Directing the functionality of molecules, materials and biophysical systems is challenging both from fundamental and applied standpoints. For example, understanding the elementary processes responsible for light-induced transformations require watching electronic and structural reorganizations on their intrinsic timescales. The X-ray free electron lasers (X-FEL) represent a new generation of incredibly short and ultra-bright X-ray source, which open new possibilities for developing the multidisciplinary field of ultrafast science. Experiments around X-FEL provide probes, sensitive to electronic and structural reorganizations, able to monitor transformations on the femtosecond timescale (1 fs=10-15  s). Recent years have seen terrific successes in providing a detailed view on light-induced processes, compared to what was understood from conventional optical pump-probe spectroscopy. This Concept article aims at illustrating, through recent studies mainly focussing on light-induced excited spin state trapping, how these X-FEL based techniques can help understanding light-activated functions, by monitoring elementary electronic and structural processes that may occur beyond the Born-Oppenheimer approximation.

Solvatomorphism-Induced 45 K Hysteresis Width in a Spin-Crossover Mononuclear Compound.

Spin-transition compounds are coordination complexes that can present two stable or metastable high-spin and low-spin states at a given temperature (thermal hysteresis). The width of the thermal hysteresis (difference between the maximum and minimum temperature between which the compound exhibits bi-stability) depends on the interactions between the coordination complexes within the compound, and which may be modulated by the absence or presence of solvent within the structure. The new compound [Fe(3-bpp)2 ][Au(CN)2 ]2 (1, 3-bpp=2,6-di-(1H-pyrazol-3-yl)pyridine) was synthesized and its properties were compared with those of the solvated compound [Fe(3-bpp)2 ][Au(CN)2 ]2 ⋅2 H2 O (1.H2 O) already described. 1 has a two-steps thermal hysteresis of 45 K, in contrast to the compound 1.H2 O which exhibits a gradual conversion without hysteresis. This hysteretic transition is accompanied by a reversible reconstructive structural transition and twinning. This stepped behaviour is also observed in the photomagnetic properties despite the low efficiency of photoswitching. Single-crystal photocrystallographic investigations confirm this low conversion, which we attributed to the high energy cost to form the high-spin structure, whose symmetry differs from that of the low-spin phase.

Electronic and Structural Dynamics During the Switching of the Photomagnetic Complex [Fe(L222 N5 )(CN)2 ].

The [Fe(L222 N5 )(CN)2 ] compound, where L222 N5 refers to the macrocyclic Schiff-base ligand, 2,13-dimethyl-3,6,9,-12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,- 16-pentaene, is a photomagnetic FeII based coordination compound, which undergoes light-induced excited spin-state trapping (LIESST). The low spin state is hexacoordinated and the high spin state heptacoordinated. This system also serves as complex for the design of trinuclear or one-dimensional compounds made of other types of bricks with diverse coordinated metals. Here its ultrafast spin-state photoswitching dynamics are studied, by combining femtosecond optical spectroscopy and femtosecond X-ray absorption measurements at the XPP station of the X-ray free-electron laser LCLS. DFT and TD-DFT calculations are used to interpret experimental findings. These studies, performed in the solution phase, show that LIESST in [Fe(L222 N5 )(CN)2 ] occurs on the 100 fs timescale under different types of photoexcitation. In addition, coherent oscillations were observed, resulting from the structural dynamics accompanying LIESST, which were recently evidenced in more conventional octahedral FeII N6 systems.

Spin Crossover Behavior in a Homologous Series of Iron(II) Complexes Based on Functionalized Bipyridyl Ligands.

A series of bulky substituted bipyridine-related iron(II) complexes [Fe(H2Bpz2)2(L)] (pz = pyrazolyl) were prepared, where L = 5,5'-dimethyl-2,2'-bipyridine (bipy-CH3, 1), L = dimethyl-2,2'-bipyridyl-5,5'-dicarboxylate (MeObpydc, 2), L = diethyl-2,2'-bipyridyl-5,5'-dicarboxylate (EtObpydc, 3), or L = diisopropyl-2,2'-bipyridine-5,5'-dicarboxylate ( i-PrObpydc, 4). The crystal structures of five new iron(II) complexes were determined by X-ray diffraction: those of 1, 3, and 4 and two modifications of 3 (3B) and 4 (4B). Complexes 1 and 3B display incomplete spin crossover (SCO) behavior because of a freezing-in effect, whereas 3 and 4B undergo gradual and incomplete SCO behaviors. Complexes 2 and 4 show a completely gradual and steep SCO, respectively. Such different SCO behaviors can be attributed to an electronic substituent effect in the bipyridyl ligand conformation and a crystal packing effect. Importantly, the electronic substituent effect of the isopropyl acetate group and C-H···O supramolecular interactions in 4 contribute to a highly cooperative behavior, which leads to an abrupt thermally induced spin transition.

Elastically driven cooperative response of a molecular material impacted by a laser pulse.

Photoinduced phase transformations occur when a laser pulse impacts a material, thereby transforming its electronic and/or structural orders, consequently affecting the functionalities. The transient nature of photoinduced states has thus far severely limited the scope of applications. It is of paramount importance to explore whether structural feedback during the solid deformation has the capacity to amplify and stabilize photoinduced transformations. Contrary to coherent optical phonons, which have long been under scrutiny, coherently propagating cell deformations over acoustic timescales have not been explored to a similar degree, particularly with respect to cooperative elastic interactions. Herein we demonstrate, experimentally and theoretically, a self-amplified responsiveness in a spin-crossover material during its delayed volume expansion. The cooperative response at the material scale prevails above a threshold excitation, significantly extending the lifetime of photoinduced states. Such elastically driven cooperativity triggered by a light pulse offers an efficient route towards the generation and stabilization of photoinduced phases in many volume-changing materials.