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.

Sequential Activation of Molecular Breathing and Bending during Spin-Crossover Photoswitching Revealed by Femtosecond Optical and X-Ray Absorption Spectroscopy.

We study the basic mechanisms allowing light to photoswitch at the molecular scale a spin-crossover material from a low- to a high-spin state. Combined femtosecond x-ray absorption performed at LCLS X-FEL and optical spectroscopy reveal that the structural stabilization of the photoinduced high-spin state results from a two step structural trapping. Molecular breathing vibrations are first activated and rapidly damped as part of the energy is sequentially transferred to molecular bending vibrations. During the photoswitching, the system follows a curved trajectory on the potential energy surface.

An investigation of photo- and pressure-induced effects in a pair of isostructural two-dimensional spin-crossover framework materials.

Two new isostructural iron(II) spin-crossover (SCO) framework (SCOF) materials of the type [Fe(dpms)2(NCX)2] (dpms = 4,4'-dipyridylmethyl sulfide; X = S (SCOF-6(S)), X = Se (SCOF-6(Se))) have been synthesized. The 2D framework materials consist of undulating and interpenetrated rhomboid (4,4) nets. SCOF-6(S) displays an incomplete SCO transition with only approximately 30 % conversion of high-spin (HS) to low-spin iron(II) sites over the temperature range 300-4 K (T1/2 = 75 K). In contrast, the NCSe(-) analogue, SCOF-6(Se), displays a complete SCO transition (T1/2 = 135 K). Photomagnetic characterizations reveal quantitative light- induced excited spin-state trapping (LIESST) of metastable HS iron(II) sites at 10 K. The temperature at which the photoinduced stored information is erased is 58 and 50 K for SCOF-6(S) and SCOF-6(Se), respectively. Variable-pressure magnetic measurements were performed on SCOF-6(S), revealing that with increasing pressure both the T1/2 value and the extent of spin conversion are increased; with pressures exceeding 5.2 kbar a complete thermal transition is achieved. This study confirms that kinetic trapping effects are responsible for hindering a complete thermally induced spin transition in SCOF-6(S) at ambient pressure due to an interplay between close T1/2 and T(LIESST) values.

Spin-state ordering on one sub-lattice of a mononuclear iron(III) spin crossover complex exhibiting LIESST and TIESST.

The two-step spin crossover in mononuclear iron(III) complex [Fe(salpm)2 ]ClO4 ⋅0.5 EtOH (1) is shown to be accompanied by a structural phase transition as concluded from (57) Fe Mössbauer spectroscopy and single crystal X-ray diffraction, with spin-state ordering on just one of two sub-lattices in the intermediate magnetic and structural phase. The complex also exhibits thermal- and light-induced spin-state trapping (TIESST and LIESST), and relaxation from the LIESST and TIESST excited states occurs via the broken symmetry intermediate phase. Two relaxation events are evident in both experiments, that is, two T(LIESST) and two T(TIESST) values are recorded. The change in symmetry which accompanies the TIESST effect was followed in real time using single crystal diffraction. After flash freezing at 15 K the crystal was warmed to 40 K at which temperature superstructure reflections were observed to appear and disappear within a 10 000 s time range. In the frame of the international year of crystallography, these results illustrate how X-ray diffraction makes it possible to understand complex ordering phenomena.

Thermal- and light-induced spin-crossover bistability in a disrupted Hofmann-type 3D framework.

The expected 3D and 2D topologies resulting from combining approximately linear bis- or monopyridyl ligands with [Fe(II)M(II)(CN)4] (M(II) = Pt, Pd, Ni) 4,4-grid sheets are well established. We show here the magnetic and structural consequences of incorporating a bent bispyridyl linker ligand in combination with [Fe(II)Pt(II)(CN)4] to form the material [Fe(H2O)2Fe(DPSe)2(Pt(CN)4)2]·3EtOH (DPSe = 4,4'-dipyridylselenide). Structural investigations reveal an unusual connectivity loosely resembling a 3D Hofmann topology where (1) there are two distinct local iron(II) environments, [Fe(II)N6] (Fe1) and [Fe(II)N4O2] (Fe2), (2) as a consequence of axial water coordination to Fe2, there are "holes" in the [Fe(II)Pt(II)(CN)4] 4,4 sheets because of some of the cyanido ligands being terminal rather than bridging, and (3) bridging of adjacent sheets occurs only through one in two DPSe ligands, with the other acting as a terminal ligand binding through only one pyridyl group. The magnetic properties are defined by this unusual topology such that only Fe1 is in the appropriate environment for a high-spin to low-spin transition to occur. Magnetic susceptibility data reveal a complete and abrupt hysteretic spin transition (T(1/2)↓ = 120 K and T(1/2)↑ = 130 K) of this iron(II) site; Fe2 remains high-spin. This material additionally exhibits a photomagnetic response (uncommon for Hofmann-related materials), showing light-induced excited spin-state trapping [LIESST; T(LIESST) = 61 K] with associated bistability evidenced in a hysteresis loop (T(1/2)↓ = 60 K and T(1/2)↑ = 66 K).

Solvate-dependent spin crossover and exchange in cobalt(II) oxazolidine nitroxide chelates.

Two oxazolidine nitroxide complexes of cobalt(II), [Co(II)(L(•))2](B(C6F5)4)2·CH2Cl2 (1) and [Co(II)(L(•))2](B(C6F5)4)2·2Et2O (2), where, L(•) is the tridentate chelator 4,4-dimethyl-2,2-bis(2-pyridyl)oxazolidine N-oxide, have been investigated by crystallographic, magnetic, reflectivity, and theoretical (DFT) methods. This work follows on from a related study on [Co(II)(L(•))2](NO3)2 (3), a multifunctional complex that simultaneously displays magnetic exchange, spin crossover, and single molecule magnetic features. Changing the anion and the nature of solvation in the present crystalline species leads to significant differences, not only between 1 and 2 but also in comparison to 3. Structural data at 123 and 273 K, in combination with magnetic data, show that at lower temperatures 1 displays low-spin Co(II)-to-radical exchange with differences in fitted J values in comparison to DFT (broken symmetry) calculated J values ascribed to the sensitive influence of a tilt angle (θ) formed between the Co(dz(2)) and the trans-oriented O atoms of the NO radical moieties in L(•). Spin crossover in 1 is evident at higher temperatures, probably influenced by the solvate molecules and crystal packing arrangement. Complex 2 remains in the high-spin Co(II) state between 2 and 350 K and undergoes antiferromagnetic exchange between Co-radical and radical-radical centers, but it is difficult to quantify. Calculations of the magnetic orbitals, eigenvalue plots, and the spin densities at the Co and radical sites in 1 and 2 have yielded satisfying details on the mechanism of metal-radical and radical-radical exchange, the radical spins being in π*NO orbitals.

Stimuli responsive hybrid magnets: tuning the photoinduced spin-crossover in Fe(III) complexes inserted into layered magnets.

The insertion of a [Fe(sal2-trien)](+) complex cation into a 2D oxalate network in the presence of different solvents results in a family of hybrid magnets with coexistence of magnetic ordering and photoinduced spin-crossover (LIESST effect) in compounds [Fe(III)(sal2-trien)][Mn(II)Cr(III)(ox)3]·CHCl3 (1·CHCl3), [Fe(III)(sal2-trien)][Mn(II)Cr(III)(ox)3]·CHBr3 (1·CHBr3), and [Fe(III)(sal2-trien)][Mn(II)Cr(III)(ox)3]·CH2Br2 (1·CH2Br2). The three compounds crystallize in a 2D honeycomb anionic layer formed by Mn(II) and Cr(III) ions linked through oxalate ligands and a layer of [Fe(sal2-trien)](+) complexes and solvent molecules (CHCl3, CHBr3, or CH2Br2) intercalated between the 2D oxalate network. The magnetic properties and Mössbauer spectroscopy indicate that they undergo long-range ferromagnetic ordering at 5.6 K and a spin crossover of the intercalated [Fe(sal2-trien)](+) complexes at different temperatures T1/2. The three compounds present a LIESST effect with a relaxation temperature TLIESST inversely proportional to T1/2. The isostructural paramagnetic compound, [Fe(III)(sal2-trien)][Zn(II)Cr(III)(ox)3]·CH2Cl2 (2·CH2Cl2) was also prepared. This compound presents a partial spin crossover of the inserted Fe(III) complex as well as a LIESST effect. Finally, spectroscopic characterization of the Fe(III) doped compound [Ga0.99Fe0.01(sal2trien)][Mn(II)Cr(III)(ox)3]·CH2Cl2 (3·CH2Cl2) shows a gradual and complete thermal spin crossover and a LIESST effect on the isolated Fe(III) complexes. This result confirms that cooperativity is not a necessary condition to observe the LIESST effect in an Fe(III) compound.

Thermal spin crossover and LIESST effect observed in complexes [Fe(L(Ch))2(NCX)2] [L(Ch) = 2,5-di(2-pyridyl)-1,3,4-chalcadiazole; Ch = O, S, Se; X = S, Se, BH3].

Two new complexes belonging to the family [Fe(II)(L)2(NCX)2] have been synthesized and structurally characterized. Complexation of the ligand L(O) = 2,5-di(2-pyridyl)-1,3,4-oxadiazole results in the formation of two derivatives of [Fe(II)(L(O))2(NCS)2] (1) with the common s-trans and the rarely observed s-cis conformation. No thermal spin crossover (SCO) was observed for the amorphous bulk material of the mixture. Using the new ligand L(Se) = 2,5-di(2-pyridyl)-1,3,4-selenadiazole, compound [Fe(II)(L(Se))2(NCS)2]·1.4DCM·0.6MeOH (2·1.4DCM·0.6MeOH) was structurally characterized by single crystal X-ray diffraction. Bulk material of [Fe(II)(L(Se))2(NCS)2]·MeOH (2·MeOH) exhibits a thermally induced SCO with small hysteresis [T(1/2)(↓) = 91 K, T(1/2)(↑) = 96 K]. LIESST and reflectivity studies have been performed on the SCO complexes [Fe(II)(L(S))2(NCS)2], [Fe(II)(L(S))2(NCSe)2], [Fe(II)(L(S))2(NCBH3)2]·H2O [L(S) = 2,5-di(2-pyridyl)-1,3,4-thiadiazole], and 2·MeOH. All complexes belong to the T0 = 90 K line [T(LIESST) = T0 - 0.3T(1/2)]. [Fe(II)(L(S))2(NCS)2], that exhibits a two-stepped thermal SCO process, has been found to also exhibit two well-separated T(LIESST) temperatures [T(LIESST, 1) = 44 K; T(LIESST, 2) = 53 K].

Synergy between polymorphism, pressure, spin-crossover and temperature in [Fe(PM-BiA)2(NCS)2]: a neutron powder diffraction investigation.

The pressure dependencies of the lattice parameters of the spin transition compound [Fe(PM-BiA)2(NCS)2] have been derived from neutron powder diffraction measurements at low temperature. The study of the compound [Fe(PM-BiA)2(NCS)2]-pI has first confirmed the atypical spin crossover behaviour under pressure of this compound that shows a pressure induced structural transition inducing the transformation into a different polymorph, [Fe(PM-BiA)2(NCS)2]-pII. This phenomenon avoids a first-order spin transition in favour of continuous transition around 0.75 GPa at ambient temperature. Low temperature measurements under pressure up to 1.07 GPa allowed us not only to describe the spin-crossover for both polymorphs but also to reach phase-diagram regions where both polymorphs co-exist in different spin-states. Finally, the reversibility of the structural variations has been demonstrated.

Spin crossover complexes [Fe(NH2trz)3](X)2·nH2O investigated by means of polarized Raman scattering and DFT calculations.

Vibrational spectra of the spin crossover (SCO) polymers [Fe(NH2trz)3](X)2·nH2O where NH2trz = 4-NH2-1,2,4-triazole and X = Cl, Br, BF4, and NO3 have been analyzed. Our results show that the anions and water molecules have no significant influence on the vibrational properties of the Fe(NH2-trz)3 polymer chains. A detailed study of the nitrate derivative, based on the DFT analysis of the polarized spectra of single crystals, has been undertaken to propose the normal mode assignment of the Raman peaks in the low spin state of the compound. Changes in the Raman spectra in the high spin state could therefore be analyzed and interpreted by several Raman bands identified as molecular probes of the SCO phenomenon. Various factors (laser power, humidity, pressure) that influence the transition temperatures and the hysteresis loops have been identified and adjusted for obtaining reliable measurements. We demonstrate in particular that all the techniques used to probe the phase transition process give comparable results providing that the sample environment is well controlled.

Photomagnetism of a sym-cis-dithiocyanato iron(II) complex with a tetradentate N,N'-bis(2-pyridylmethyl)1,2-ethanediamine ligand.

A comprehensive study of the magnetic and photomagnetic behaviors of cis-[Fe(picen)(NCS)(2) ] (picen = N,N'-bis(2-pyridylmethyl)1,2-ethanediamine) was carried out. The spin-equilibration was extremely slow in the vicinity of the thermal spin-transition. When the cooling speed was slower than 0.1 K min(-1), this complex was characterized by an abrupt thermal spin-transition at about 70 K. Measurement of the kinetics in the range 60-70 K was performed to approach the quasi-static hysteresis loop. At low temperatures, the metastable HS state was quenched by a rapid freezing process and the critical T(TIESST) temperature, which was associated with the thermally induced excited spin-state-trapping (TIESST) effect, was measured. At 10 K, this complex also exhibited the well-known light-induced excited spin-state-trapping (LIESST) effect and the T(LIESST) temperature was determined. The kinetics of the metastable HS states, which were generated from the freezing effect and from the light-induced excitation, was studied. Single-crystal X-ray diffraction as a function of speed-cooling and light conditions at 30 K revealed the mechanism of the spin-crossover in this complex as well as some direct relationships between its structural properties and its spin state. This spin-crossover (SCO) material represents a fascinating example in which the metastability of the HS state is in close vicinity to the thermal spin-transition region. Moreover, it is a beautiful example of a complex in which the metastable HS states can be generated, and then compared, either by the freezing effect or by the LIESST effect.

One-step vs stepwise immobilization of 1-D coordination-based Rh-Rh molecular wires on gold surfaces.

Reaction of dimeric [Rh(II)(2)(phen)(2)(µ-OAc)(2)(MeCN)(2)](BF(4))(2) (phen =1,10-phenanthroline) with pyrazine (pz) in a 1:2 ratio leads to the new 1-D metal-metal-bonded coordination oligomer {[Rh(II)(2)(phen)(2)(µ-OAc)(2)(pz)](BF(4))(2)}(n) (Rh-Rhpz)(n) (1), where each Rh atom of the dimeric unit (Rh-Rh) is coordinated in the equatorial plane to a nitrogen atom of a rigid and linear bifunctionalized organic linker (pz). Single X-ray diffraction analysis reveals the 1-D straight oligomeric chain structure (molecular wire, MW) consists of alternating (Rh-Rh) units and pz linking ligands with free BF(4)(-) as counteranions, and each metal center has a slightly distorted octahedral arrangement. The presence of accessible labile MeCN groups on both ends of these MWs ("free ends") enables functionalization of a 4-mercaptopyridine-gold coordinating platform (Au/MP) to form in one step a layer of coordination oligomer (Au/MP(Rh-Rhpz)(n); n ≈ 50). Furthermore (Rh-Rhpz)(n) (n = 1-6) MWs were grafted to Au/MP surfaces by a conventional step-by-step assembly construction involving coordination reactions between the Rh dimer ([Rh(2)(phen)(2)(µ-OAc)(2)(MeCN)(2)](BF(4))(2) (2)) and pz. A detailed physicochemical study (UV-vis, RAIR, QCM-D, ellipsometry, contact angle measurements, as well as impedance spectroscopy and cyclic voltammetry) has been made during both assembly methods to characterize the resulting surface-anchored coordination molecular wire (CMW) layers (Au/MP(Rh-Rhpz)(n)). The results indicate that the immobilized molecular assemblies (MAs) were successfully fabricated using both methods of assembly. The efficiency of the two methods is discussed.

Spectroscopic and magnetic properties of the metastable states in the coordination network [{Co(prm)2}2{Co(H2O)2}{W(CN)8}2]·4H2O (prm = pyrimidine).

The study of the metastable states, obtained by thermal quenching or by light irradiation in the [{Co(prm)(2)}(2){Co(H(2)O)(2)}{W(CN)(8)}(2)]·4H(2)O complex, is reported using powder X-ray diffraction, Raman spectroscopy, optical reflectivity, and magnetic measurements. This compound is characterized by a electron-transfer (ET) phase transition occurring between a high-temperature phase (HT phase) formed by paramagnetic Co(II)-W(V) units and a low-temperature phase (LT phase) formed by diamagnetic Co(III)-W(IV) units. Metastable phases can be induced at low temperature either by thermal quenching rapidly cooling phase named RC or by irradiation photo-induced phase named PI similar to the well-known Light-Induced Excited Spin State Trapping effect. The relaxation dynamics of the metastable phases have been studied and revealed some differences between the RC and PI phases. The sigmoidal shape of the relaxation curves in the RC phase is in agreement with the cooperative nature of the process. Thermodynamic parameters that govern the relaxation have been determined and used to reproduce the experimental Thermal-Induced Excited Spin State Trapping curve.

High-pressure spin-crossover in a dinuclear Fe(II) complex.

The effect of pressure on the dinuclear spin crossover material [{Fe(bpp)(NCS)(2)}(2)(4,4'-bipy)]·2MeOH (where bpp = 2,6-bis(pyrazol-3-yl)pyridine and 4,4'-bipy = 4,4'-bipyridine, 1) has been investigated with single crystal X-ray diffraction and Raman spectroscopy using diamond anvil cell techniques. The very gradual pressure-induced spin crossover occurs between 7 and 25 kbar, and shows no evidence of crystallographic phase transitions. The pressure-induced spin transition leads to a complete LS state which is not thermally accessible. This structural evolution under pressure is in stark contrast to the previously reported thermal spin crossover behaviour, in which a symmetry-breaking, purely structural phase transition results in only partial conversion to the low spin state. This observation is attributed to the symmetry-breaking phase transition becoming unfavourable under pressure.

Antagonism between extreme negative linear compression and spin crossover in [Fe(dpp)(2)(NCS)(2)]⋠py.

A scissor-like geometric mechanism is responsible for the strongest negative linear compression effect yet observed in a molecular material, [Fe(dpp)(2)(NCS)(2)]⋅py (see picture; dpp=dipyrido[3,2-a:2'3'-c]phenazine), C gray, N blue, S yellow, Fe red). The same mechanism is also responsible for suppressing the high-spin to low-spin transition under pressure.

Analysis of the photomagnetic properties of cyano-bridged heterobimetallic complexes by X-ray diffraction.

Single crystal synchrotron X-ray diffraction measurements have been carried out on [Nd(DMF)(4)(H(2)O)(3)(µ-CN)Fe(CN)(5)]·H(2)O (DMF = dimethyl-formamide), 1; [Y(DMF)(4)(H(2)O)(3)(µ-CN)Fe(CN)(5)]·H(2)O, 2; [Ce(DMF)(4)(H(2)O)(3)(µ-CN)Fe(CN)(5)]·H(2)O, 3; [Sm(DMF)(4)(H(2)O)(3)(µ-CN)Fe(CN)(5)]·H(2)O, 4; [Tb(DMF)(4)(H(2)O)(3)(µ-CN)Fe(CN)(5)]·H(2)O, 5; [Yb(DMF)(4)(H(2)O)(3)(µ-CN)Fe(CN)(5)]·H(2)O, 6; and [Nd(DMF)(4)(H(2)O)(3)(µ-CN)Co(CN)(5)]·H(2)O, 7, at 15(2) K with and without UV illumination of the crystals. Significant changes in unit cell parameters are observed for all of the iron-containing complexes, while compound 7 shows no response to UV illumination. These results are consistent with previous results and are furthermore reproduced by powder synchrotron X-ray diffraction for compounds 1 and 7. Photoexcited crystal structures have been determined for 1-6 from refinements of two-conformer models, and excited state occupancies in the range 80-94% are found. Significant bond length changes are observed for the Fe-ligand bonds (up to 0.06 Å), the cyano bonds (up to 0.02 Å), and the lanthanide-ligand bonds (up to 0.1 Å). On the contrary, powder X-ray diffraction on the simple compound K(3)Fe(CN)(6), 8, upon UV illumination does not show any structural changes, suggesting that the photomagnetic effect requires the presence of both the transition metal and the lanthanide ion. Photomagnetic measurements show an increase in magnetization of the excited state of 1 of up to 3%, which is much diminished compared with previously published values of 45%. Furthermore, they show that the isostructural complex [La(DMF)(4)(H(2)O)(3)(µ-CN)Fe(CN)(5)]·H(2)O, 9, exhibits identical magnetic responses in the UV-induced excited crystal structure.

Two-step thermal spin transition and LIESST relaxation of the polymeric spin-crossover compounds Fe(X-py)2[Ag(CN)2]2 (X=H, 3-methyl, 4-methyl, 3,4-dimethyl, 3-Cl).

In the series of polymeric spin-crossover compounds Fe(X-py)(2)[Ag(CN)(2))](2) (py=pyridine, X=H, 3-Cl, 3-methyl, 4-methyl, 3,4-dimethyl), magnetic and calorimetric measurements have revealed that the conversion from the high-spin (HS) to the low-spin (LS) state occurs by two-step transitions for three out of five members of the family (X=H, 4-methyl, and X=3,4-dimethyl). The two other compounds (X=3-Cl and 3-methyl) show respectively an incomplete spin transition and no transition at all, the latter remaining in the HS state in the whole temperature range. The spin-crossover behaviour of the compound undergoing two-step transitions is well described by a thermodynamic model that considers both steps. Calculations with this model show low cooperativity in this type of systems. Reflectivity and photomagnetic experiments reveal that all of the compounds except that with X=3-methyl undergo light-induced excited spin state trapping (LIESST) at low temperatures. Isothermal HS-to-LS relaxation curves at different temperatures support the low-cooperativity character by following an exponential decay law, although in the thermally activated regime and for aX=H and X=3,4-dimethyl the behaviour is well described by a double exponential function in accordance with the two-step thermal spin transition. The thermodynamic parameters determined from this isothermal analysis were used for simulation of thermal relaxation curves, which nicely reproduce the experimental data.

Thermal- and light-induced spin crossover in a guest-dependent dinuclear iron(II) system.

We previously reported the dinuclear material [Fe(II) (2)(ddpp)(2)(NCS)(4)] x 4 CH(2)Cl(2) (1 x 4 CH(2)Cl(2); ddpp = 2,5-di(2',2''-dipyridylamino)pyridine) and its partially desolvated analogue (1 x CH(2)Cl(2)), which undergo two- and one-step spin-crossover (SCO) transitions, respectively. Here, we manipulate the type and degree of solvation in this system and find that either a one- or two-step spin transition can be specifically targeted. The chloroform clathrate 1 x 4 CHCl(3) undergoes a relatively abrupt one-step SCO, in which the two equivalent Fe(II) sites within the dinuclear molecule crossover simultaneously. Partial desolvation of 1 x 4 CHCl(3) to form 1 x 3 CHCl(3) and 1 x CHCl(3) occurs through single-crystal-to-single-crystal processes (monoclinic C2/c to P2(1)/n to P2(1)/n) in which the two equivalent Fe(II) sites become inequivalent sites within the dinuclear molecule of each phase. Both 1 x 3 CHCl(3) and 1 x CHCl(3) undergo one-step spin transitions, with the former having a significantly higher SCO temperature than 1 x 4 CHCl(3) and the latter, and each has a broader SCO transition than 1 x 4 CHCl(3), attributable to the overlap of two SCO steps in each case. Further magnetic manipulation can be carried out on these materials through reversibly resolvating the partially desolvated material with chloroform to produce the original one-step SCO, or with dichloromethane to produce a two-step SCO reminiscent of that seen for 1 x 4 CH(2)Cl(2). Furthermore, we investigate the light-induced excited spin state trapping (LIESST) effect on 1 x 4 CH(2)Cl(2) and 1 x CH(2)Cl(2) and observe partial LIESST activity for the former and no activity for the latter.

Cyanocarbanion-based spin-crossover materials: photocrystallographic and photomagnetic studies of a new iron(II) neutral chain.

A new iron(II) chain of formula [Fe(abpt)(2)(tcpd)] [1; (tcpd)(2-) = [C(10)N(6)](2-) = (C[C(CN)(2)](3))(2-) = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide anion, abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole] has been synthesized and characterized by IR spectroscopy, detailed variable-temperature single-crystal X-ray diffraction, magnetic and photomagnetic measurements. The crystal structure determination of 1 reveals a one-dimensional structural architecture in which the (tcpd)(2-) cyanocarbanion acts as a µ(2)-bridging ligand and the two abpt molecules act as chelating ligands. Detailed X-ray diffraction studies as a function of the temperature (293-10 K) showed a strong modification of the iron coordination sphere, whose characteristics are in agreement with the presence of a spin-crossover transition from high spin (HS) to low spin (LS) in 1. The average Fe-N distances at room temperature, at 10 K following a flash cooling, and at 10 K after subsequent HS-to-LS relaxation are in the range expected for 100%, 50%, and 25% fractions of HS Fe(II), respectively. These observations are consistent with the presence of ca. 25% residual HS species at low temperatures, as derived from the magnetic data. The signature of a photoinduced metastable HS state in 1 has been detected by performing coupled photomagnetic and photocrystallographic analyses. The limiting T(LIESST) value associated with the light-induced excited-spin-state trapping effect was derived as 35 K, in good agreement with the thermal dependence of the unit cell volume upon irradiation. Kinetic studies governing the photoinduced HS/LS process have been recorded at different temperatures; a reverse-LIESST effect has been evidenced at 10 K as a reduction of the residual HS fraction by irradiating the sample at 830 nm.

Mechanism for optical switching of the spin crossover [Fe(NH(2)-trz)(3)](Br)(2).3H(2)O compound at room temperature.

This paper reports on phase transition photo-induced by a nanosecond laser pulse in the molecular spin crossover material [Fe(NH(2)-trz)(3)] (Br)(2).3H(2)O (with NH(2)trz = 4-amino-1,2,4-triazole) around room temperature and in the close vicinity of the thermal hysteresis loop. The measurements are carried out using a time-resolved pump-probe experiment and by recording the reflectivity change at various temperatures and laser intensities. The dynamics of the optically induced reflectivity changes are presented and discussed. We propose a simple model that describes well the recorded phenomena. It takes into account the physical and optical properties of the sample that directly impact the amplitude and the dynamics of the laser-induced heating of the compound.