Photoselective MLCT to d-d pathways for light-induced excited spin state trapping.

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.

Pressure-induced switching properties of the iron(iii) spin-transition complex [FeIII(3-OMeSalEen)2]PF6.

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.

Comparison of structural dynamics and coherence of d-d and MLCT light-induced spin state trapping.

Light-induced excited spin state trapping (LIESST) in FeII spin-crossover systems is a process that involves the switching of molecules from low (LS, S = 0) to high spin (HS, S = 2) states. The direct LS-to-HS conversion is forbidden by selection rules, and LIESST involves intermediate states such as 1,3MLCT or 1,3T. The intersystem crossing sequence results in an HS state, structurally trapped by metal-ligand bond elongation through the coherent activation and damping of molecular breathing. The ultrafast dynamics of this process has been investigated in FeN6 ligand field systems, under MLCT excitation. Herein, we studied LIESST in an FeIIN4O2 spin-crossover material of lower symmetry, which allowed for quite intense and low-energy shifted d-d bands. By combining ab initio DFT and TD-DFT calculations and fs optical absorption measurements, we demonstrated that shorter intermediates enhanced coherent structural dynamics, and d-d excitation induced faster LS-to-HS switching, compared to MLCT.

Nanocrystals of Fe(phen)2(NCS)2 and the size-dependent spin-crossover characteristics.

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.

Successive dynamical steps of photoinduced switching of a molecular Fe(III) spin-crossover material by time-resolved x-ray diffraction.

We investigate the out-of-equilibrium switching dynamics of a molecular Fe(III) spin-crossover solid triggered by a femtosecond laser flash. The time-resolved x-ray diffraction and optical results show that the dynamics span from subpicosecond local photoswitching followed by volume expansion (nanosecond) and thermal switching (microsecond). We present a physical picture of the consecutive steps in the photoswitching of molecular materials.

Ligand-driven light-induced spin change activity and bidirectional photomagnetism of styrylpyridine iron(II) complexes in polymeric media.

Two pseudo-octahedral iron(II) complexes, Fe(stpy)(4)(NCSe)(2), containing photoresponsive ligands (cis <--> trans isomerization of -CHCH-) were prepared with trans- or cis-styrylpyridine (stpy) isomers. The magnetic behavior of the polycrystalline solids was previously shown to depend on the configuration of the stpy ligand. The crystal X-ray structures were determined at 293 and 104 K for both isomers. The all-trans and all-cis compounds crystallize in the orthorhombic (Pna2(1)) and the monoclinic space groups (C2/c), respectively. No symmetry change occurs upon cooling to 104 K. The Fe(II) centers lie in axially compressed octahedra with NCSe anions in the apical position and the four pyridinic nitrogens in the meridional plane. The variation of metal-ligand bond lengths as a function of temperature reflects the thermal S = 0 <--> S = 2 crossover of all-trans complexes and the S = 2 ground state of all-cis complexes. The unit-cell volumes per metal ion also change accordingly, and the relative variation due to the spin-crossover compares those associated with the formal change of configuration of the four stpy isomers. The photomagnetic responses were investigated at 130 K with doped polymer thin films containing all-cis (high-spin) or all-trans species (partly low-spin). The 130 K illumination of these doped poly(methyl methacrylate) (PMMA) films leads to the UV-vis absorption features typical for the cis <--> trans photoisomerization of the stilbenoid moiety. The direct magnetic measurements have unambiguously established the photomagnetic effect named ligand-driven light-induced spin change (LD-LISC). The 355 nm excitation of doped thin films produces very long lifetime states that are manifested by high-spin to low-spin (all-cis complex) and low-spin to high-spin (all-trans complex) changes of the Fe(II) magnetic behavior; the process is bidirectional. A structural analysis based on the single-crystal X-ray diffraction data has been proposed to rationalize the LD-LISC activity detected here for doped PMMA thin films.

Combining organic photochromism with inorganic paramagnetism--optical tuning of the iron(II) electronic structure.

The crystalline photochromism of a diarylethene pyridyl ligand is applied to the modulation of the electronic environment of a high-spin Fe(II) metal ion.

Spin crossover of ferric complexes with catecholate derivatives. Single-crystal X-ray structure, magnetic and Mössbauer investigations.

Complexes of general formula [(TPA)Fe(R-Cat)]X.nS were synthesised with different catecholate derivatives and anions (TPA = tris(2-pyridylmethyl)amine, R-Cat2- = 4,5-(NO2)2-Cat2- denoted DNC(2-); 3,4,5,6-Cl4-Cat2- denoted TCC2-; 3-OMe-Cat(2-); 4-Me-Cat(2-) and X = BPh4-; NO3-; PF6-; ClO4-; S = solvent molecule). Their magnetic behaviours in the solid state show a general feature along the series, viz., the occurrence of a thermally-induced spin crossover process. The transition curves are continuous with transition temperatures ranging from ca. 84 to 257 K. The crystal structures of [(TPA)Fe(DNC)]X (X = PF6-; BPh4-) and [(TPA)Fe(TCC)]X.nS (X = PF6-; NO3- and n= 1, S = H2O; ClO4- and n= 1, S = H2O; BPh4- and n= 1, S = C3H6O) were solved at 100 (or 123 K) and 293 K. For those two systems, the characteristics of the [FeN(4)O(2)] coordination core and those of the dioxolene ligands appear to be consistent with a prevailing Fe(III)-catecholate formulation. This feature is in contrast with the large quantum mixing between Fe(III)-catecholate and Fe(II)-semiquinonate forms recently observed with the more electron donating simple catecholate dianion. The thermal spin crossover process is accompanied by significant changes of the molecular structures as shown by the average variation of the metal-ligand bond distances which can be extrapolated for a complete spin conversion from ca. 0.123 to 0.156 A. The different space groups were retained in the low- and high-temperature phases.