Maciej Lorenc

Chopper system for time resolved experiments with synchrotron radiation

A chopper system for time resolved pump-probe experiments with x-ray beams from a synchrotron is described. The system has three parts: a water-cooled heatload chopper, a high-speed chopper, and a millisecond shutter. The chopper system, which is installed in beamline ID09B at the European Synchrotron Radiation Facility, provides short x-ray pulses for pump-probe experiments with ultrafast lasers. The chopper system can produce x-ray pulses as short as 200 ns in a continuous beam and repeat at frequencies from 0 to 3 kHz. For bunch filling patterns of the synchrotron with pulse separations greater than 100 ns, the high-speed chopper can isolate single 100 ps x-ray pulses that are used for the highest time resolution. A new rotor in the high-speed chopper is presented with a single pulse (100 ps) and long pulse (10 micros) option. In white beam experiments, the heatload of the (noncooled) high-speed chopper is lowered by a heatload chopper, which absorbs 95% of the incoming power without affecting the pulses selected by the high speed chopper.

Femtosecond Spin-State Photoswitching of Molecular Nanocrystals Evidenced by Optical Spectroscopy†

In the field of control science, which aims at switching the physical properties of materials, photoinduced phase transitions open fascinating perspectives for driving a material towards a new state, far from thermal equilibrium. Such photoswitching will impact future technologies as it provides doorways to the light-control of various photoswitchable functions (for example, magnetic, optical, conducting, and ferroelectric). In control science, tailored laser pulses are widely regarded as the most likely source for achieving that goal. In that respect, the great challenge for molecularbased materials is directing the functionality, both at the relevant size and time scales. If we attempt simple parallels here, the goal is to achieve at the level of a material what femtochemistry has accomplished at the level of a molecule. In observing and understanding how materials work during elementary dynamical processes, several challenging basic questions are confronted. For instance, ultrafast information processing based on the control of light-driven switching of the physical properties of materials requires that such systems be directed through a complex pathway from atomic to material scales, and that the fundamental limits of transformation speed be overcome, or circumvented. Molecular magnets, and especially the spin-crossover compounds (SCO), are ideal candidates for photo-active prototypes, which show photomagnetic and photochromic properties driven by the switching of the constituent molecules between their electronic low spin (LS) and high spin (HS) states. Herein we report the ultrafast spin state photoswitching of a spin-crossover nanocrystal of an Fe complex, [Fe(3-MeOSalEen)2]PF6 (Figure 1), as studied through femtosecond optical spectroscopy (H-3-MeO-SalEen being the condensation product of 3-methoxy-substituted salicylaldehyde and N-ethyl-ethylenediamine). This result provides proof-of-principle for femtosecond switching at the nanoscale in SCO materials showing photomagnetic and photochromic responses. SCO materials are bistable systems, for which nanosecond laser excitation within the range of thermal hysteresis can generate LS to HS transition. Ultrafast investigations of similar photo-transformations have been mainly limited to single molecules in solution, and only recently also carried out on crystals. Despite formidable progress in the chemistry and engineering of spin-crossover nanoparticles, as well as their nano-patterning and nanoscale assembling 11] while preserving their switchable properties, the ultrafast switching of such materials has not yet been observed. Herein we study the ultrafast LS-to-HS spin-state photoswitching pathway of nanocrystals (Figure 1), taking advantage of growing knowledge in the field of ultrafast chemical physics. [*] R. Bertoni, Dr. M. Lorenc, Dr. M. Servol, Prof. E. Collet Institut de Physique de Rennes, UMR CNRS 6251 Universit Rennes 1, 35042 Rennes cedex (France) E-mail: maciej.lorenc@univ-rennes1.fr eric.collet@univ-rennes1.fr

Ultrafast spin-state photoswitching in a crystal and slower consecutive processes investigated by femtosecond optical spectroscopy and picosecond X-ray diffractionw

We report the spin state photo-switching dynamics in two polymorphs of a spin-crossover molecular complex triggered by a femtosecond laser flash, as determined by combining femtosecond optical pump-probe spectroscopy and picosecond X-ray diffraction techniques. The light-driven transformations in the two polymorphs are compared. Combining both techniques and tracking how the X-ray data correlate with optical signals allow understanding of how electronic and structural degrees of freedom couple and play their role when the switchable molecules interact in the active crystalline medium. The study sheds light on crossing the border between femtochemistry at the molecular scale and femtoswitching at the material scale.

Structural dynamics of photoinduced molecular switching in the solid state.

Fast and ultra-fast time-resolved diffraction is a fantastic tool for directly observing the structural dynamics of a material rearrangement during the transformation induced by an ultra-short laser pulse. The paper illustrates this ability using the dynamics of photoinduced molecular switching in the solid state probed by 100 ps X-ray diffraction. This structural information is crucial for establishing the physical foundations of how to direct macroscopic photoswitching in materials. A key feature is that dynamics follow a complex pathway from molecular to material scales through a sequence of processes. Not only is the pathway indirect, the nature of the dynamical processes along the pathway depends on the timescale. This dictates which types of degrees of freedom are involved in the subsequent dynamics or kinetics and which are frozen or statistically averaged. We present a recent investigation of the structural dynamics in multifunctional spin-crossover materials, which are prototypes of molecular bistability in the solid state. The time-resolved X-ray diffraction results show that the dynamics span from subpicosecond molecular photoswitching followed by volume expansion (on a nanosecond timescale) and additional thermoswitching (on a microsecond timescale).

Ultrafast Light-Induced Spin-State Trapping Photophysics Investigated in Fe(phen)2(NCS)2 Spin-Crossover Crystal

Few photoactive molecules undergo a complete transformation of physical properties (magnetism, optical absorption, etc.) when irradiated with light. Such phenomena can happen on the time scale of fundamental atomic motions leading to an entirely new state within less than 1 ps following light absorption. Spin crossover (SCO) molecules are prototype systems having the ability to switch between low spin (LS) and high spin (HS) molecular states both at thermal equilibrium and after light irradiation. In the case of Fe(II) (3d(6)) complexes in a nearly octahedral ligand field, the two possible electronic distributions among the 3d split orbitals are S = 0 for the LS diamagnetic state and S = 2 for the HS paramagnetic state. In crystals, such photoexcited states can be long-lived at low temperature, as is the case for the photoinduced HS state of the [Fe(phen)2(NCS)2] SCO compound investigated here. We first show how such bistability between the diamagnetic and paramagnetic states can be characterized at thermal equilibrium or after light irradiation at low temperature. Complementary techniques provide invaluable insights into relationships between changes of electronic states and structural reorganization. But the development of such light-active materials requires the understanding of the basic mechanism following light excitation of molecules, responsible for trapping them into new electronic and structural states. We therefore discuss how we can observe a photomagnetic molecule during switching and catch on the fly electronic and structural molecular changes with ultrafast X-ray and optical absorption spectroscopies. In addition, there is a long debate regarding the mechanism behind the efficiency of such a light-induced process. Recent theoretical works suggest that such speed and efficiency are possible thanks to the instantaneous coupling with the phonons of the final state. We discuss here the first experimental proof of that statement as we observe the instantaneous activation of one key phonon mode precluding any recurrence towards the initial state. Our studies show that the structural molecular reorganization trapping the photoinduced electronic state occurs in two sequential steps: the molecule elongates first (within 170 femtosecond) and bends afterwards. This dynamics is caught via the coherent vibrational energy transfer of the two main structural modes. We discuss the transformation pathway connecting the initial photoexcited state to the final state, which involves several key reaction coordinates. These results show the need to replace the classical single coordinate picture employed so far with a more complex multidimensional energy surface.

100 Picosecond Diffraction Catches Structural Transients of Laser‐Pulse Triggered Switching in a Spin‐Crossover Crystal

We study by 100 picosecond X-ray diffraction the photo-switching dynamics of single crystal of the orthorhombic polymorph of the spin-crossover complex [(TPA)Fe(TCC)]PF(6), in which TPA = tris(2-pyridyl methyl)amine, TCC(2-) = 3,4,5,6-Cl(4)-Catecholate(2-). In the frame of the emerging field of dynamical structural science, this is made possible by using optical pump/X-ray probe techniques, which allow following in real time structural reorganization at intra- and intermolecular levels associated with the change of spin state in the crystal. We use here the time structure of the synchrotron radiation generating 100 picosecond X-ray pulses, coupled to 100 fs laser excitation. This study has revealed a rich variety of structural reorganizations, associated with the different steps of the dynamical process. Three consecutive regimes are evidenced in the time domain: 1) local molecular photo-switching with structural reorganization at constant volume, 2) volume relaxation with inhomogeneous distribution of local temperatures, 3) homogenization of the crystal in the transient state 100 µs after laser excitation. These findings are fundamentally different from those of conventional diffraction studies of long-lived photoinduced high spin states. The time-resolution used here with picosecond X-ray diffraction probes different physical quantities on their intrinsic time-scale, shedding new light on the successive processes driving macroscopic switching in a functionalized material. These results pave the way for structural studies away from equilibrium and represent a first step toward femtosecond crystallography.

The Role of Ligand‐Field States in the Ultrafast Photophysical Cycle of the Prototypical Iron(II) Spin‐Crossover Compound [Fe(ptz)6](BF4)2

Light-induced excited spin-state trapping (LIESST) in iron(II) spin-crossover compounds, that is, the light-induced population of the high-spin (S=2) state below the thermal transition temperature, was discovered thirty years ago. For irradiation into metal-ligand charge transfer (MLCT) bands of the low-spin (S=0) species the acknowledged sequence takes the system from the initially excited (1) MLCT to the high-spin state via the (3) MLCT state within ca. 150 fs, thereby bypassing low-lying ligand-field (LF) states. Nevertheless, these play a role, as borne out by the observation of LIESST and reverse-LIESST on irradiation directly into the LF bands for systems with only high-energy MLCT states. Herein we elucidate the ultrafast reverse-LIESST pathway by identifying the lowest energy S=1 LF state as an intermediate state with a lifetime of 39 ps for the light-induced high-spin to low-spin conversion on irradiation into the spin-allowed LF transition of the high-spin species in the NIR.

Polymorphism in the spin‐crossover ferric complexes [(TPA)FeIII(TCC)]PF6

We have identified two polymorphs of the molecular complex [(TPA)Fe((III))(TCC)]PF(6) [TPA = tris(2-pyridylmethyl)amine and TCC = 3,4,5,6-tetrachlorocatecholate dianion]: one is monoclinic and the other is orthorhombic. By lowering the temperature both undergo a thermal spin-crossover between a high-spin (S = 5/2) and a low-spin (S = 1/2) state, which we detected by magnetic, optical and X-ray diffraction measurements. The thermal crossover is only slightly shifted between the polymorphs. Their crystalline structures consist of similar cation layers alternating with PF(6) anion layers, packed differently in the two polymorphs. The magnetic and optical properties of the polymorphs are presented.

Ultrafast Photoswitching in a Copper‐Nitroxide‐Based Molecular Magnet

Molecular compounds with photoswitchable magnetic properties have been intensively investigated over the last decades due to their prospective applications in nanoelectronics, sensing and magnetic data storage. The family of copper-nitroxide-based molecular magnets represents a new promising type of photoswitchable compounds. We report the first study of these appealing systems using femtosecond optical spectroscopy. We unveil the mechanism of ultrafast (<50 fs) spin state photoswitching and establish its principal differences compared to other photoswitchable magnets. On this basis, we propose potential advantages of copper-nitroxide-based molecular magnets for the future design of ultrafast magnetic materials.

State of the art and opportunities in probing photoinduced phase transitions in molecular materials by conventional and picosecond X-ray diffraction

Abstract The optical control of the macroscopic physical properties (magnetic, optical …) of a material by laser irradiation is gaining interest through the emerging field of photoinduced phase transitions. Light-induced changes of the macroscopic state of a material involves subtle coupling between the electronic and structural degrees of freedom, which are essential to stabilize the photo-excited state, different in nature from the stable state. Therefore the new experimental field of photocrystallography plays a key role. It goes far beyond simple structural analysis under laser excitation. By playing on different physical parameters and developing the techniques and analysis, one can investigate new out of equilibrium physics through light-driven cooperative dynamics and transformations in materials. This paper is reviewing different aspects of the use of photocrystallography to investigate the nature, the mechanisms and the dynamics of photoinduced phase transitions for photo-steady or long-lived states, as well as transformations driven by an ultra-short light pulse. We also give a brief overview on recent advances in time-resolved crystallography with 100 ps resolution.