Low-spin Molecules Research Articles

Metal vs Ligand Oxidation: Coexistence of Both Metal-Centered and Ligand-Centered Oxidized Species.

A series of two-electron-oxidized cobalt porphyrin dimers have been synthesized upon controlled oxidations using halogens. Rather unexpectedly, X-ray structures of two of these complexes contain two structurally different low-spin molecules in the same asymmetric unit of their unit cells: one is the metal-centered oxidized diamagnetic entity of the type CoIII(por), while the other one is the ligand-centered oxidized paramagnetic entity of the type CoII(por•+). Spectroscopic, magnetic, and DFT investigations confirmed the coexistence of the two very different electronic structures both in the solid and solution phases and also revealed a ferromagnetic spin coupling between Co(II) and porphyrin π-cation radicals and a weak antiferromagnetic coupling between the π-cation radicals of two macrocycles via the bridge in the paramagnetic complex.

Quantification of the thermodynamic effects of the low-spin - high-spin interaction in molecular crystals of a mononuclear iron(II) spin crossover complex.

A method is proposed to estimate the energetic and entropic effects of spins of neighbouring molecules on the spin transition of a mononuclear spin crossover (SCO) complex in a molecular crystal. Density functional theory (DFT) methods have been used to model the SCO material [FeII(Lnpdtz)2(NCS)2] (Lnpdtz = 2-naphthyl-5-pyridyl-1,2,4-thiadiazole) exhibiting numerous π-π interactions using a 2D arrangement of 15 molecules. The modelling considers only the effects in the crystallographical ac plane with a particularly pronounced stacking but paves the way for future work with 3D arrangements which are computational much more costly. It involves the optimisation and normal mode calculation of the molecules in a rigid matrix of both low-spin (LS) and high-spin (HS) neighbours. This procedure has been used to calculate the previously defined cooperativity parameter Hcoop (S. Rackwitz, W. Klopper, V. Schünemann and J. A. Wolny, Phys. Chem. Chem. Phys., 2013, 15, 15450). For [FeII(Lnpdtz)2(NCS)] we obtain Hcoop = 11 kJ mol-1, a value which is comparable to those found for 3D polynuclear spin crossover materials. A normal mode analysis of the optimised centrally located molecule indicates that the vibrational entropy of the spin transition is somewhat higher (5 J K-1 mol-1) for the LS to HS transition in the LS matrix than in the HS one. The calculations show that the interactions with the neighbours influence the low-frequency modes with wave numbers <65-70 cm-1. These cause the main difference in the vibrational entropy of the spin transition for the vicinity of high- and low-spin molecules. Furthermore, a deformation of the coordination sphere of the central molecule is observed when the spins of the surrounding centres are switched. This deformation is accompanied by a change in the equatorial Fe-N bond lengths.

Deposition of the Spin Crossover FeII -Pyrazolylborate Complex on Au(111) Surface at the Molecular Level.

The interaction at the molecular level of the spin-crossover (SCO) FeII ((3,5-(CH3 )2 Pz)3 BH)2 complex with the Au(111) surface is analyzed by means of rPBE periodic calculations. Our results show that the adsorption on the metallic surface enhances the transition energy, increasing the relative stability of the low spin (LS) state. The interaction indeed is spin-dependent, stronger for the low spin than the high spin (HS) state. The different strength of the Fe ligand field at low and high temperature manifests on the nature, spatial extension and relative energy of the states close to the Fermi level, with a larger metal-ligand hybridization in the LS state. This feature is of relevance for the differential adsorption of the LS and HS molecules, the spin-dependent conductance, and for the differences found in the corresponding STM images, correctly reproduced from the density of states provided by the rPBE calculations. It is expected that this spin dependence will be a general feature of the SCO molecule-substrate interaction, since it is rooted in the different ligand field of Fe site at low and high temperatures, a common hallmark of the FeII SCO complexes. Finally, the states involved in the LIESST phenomenon has been identified through NEVPT2 calculations on a model reaction path. A tentative pathway for the photoinduced LS→HS transition is proposed, that does not involve the intermediate triplet states, and nicely reproduces both the blue laser wavelength required for the activation, and the wavelength of the reverse HS → LS transition.

Cooperativity in Spin Crossover Systems. An Atomistic Perspective on the Devil's Staircase.

Cooperativity is key in defining the shape (i.e., gradual, abrupt, or hysteretic) of thermally driven spin transitions in magnetic switches. Despite its importance, there is very little information on its atomistic origin, which hinders the rational design of materials displaying a bistability region (i.e., hysteresis). In this paper, we investigate the spin transition of two solvatomorphs of [Fe(2-pic)3]Cl2, an Fe(II)-complex displaying thermal spin crossover (SCO) from a low-spin (LS) to a high-spin (HS) state with either gradual or abrupt two-step character. To do it, we apply a novel computational protocol to study the cooperativity of SCO compounds from DFT calculations, which does not rely on a priori assumptions on the studied system. The distinct shape of the spin transition is successfully captured, and the atomistic origin of cooperativity is traced back to geometrical distortions of the Fe-N6 core in case of the solvatomorph exhibiting an abrupt transition. According to our calculations, HS and LS molecules contribute differently to cooperativity, which results in a complex energetic evolution of the spin transition that cannot be described by the common Slichter-Drickamer model. The present work opens new avenues for the study of cooperativity of SCO systems having a chemically oriented perspective and demonstrates that quantum chemistry calculations can discriminate the shape of a spin transition, while providing insight into the atomistic underlying factors that contribute to its cooperative behavior.

Pressure-induced two-step spin crossover in a double-layered elastic model

We study the two-step spin crossover in a double-layered elastic model based on transition metal complexes each taking high spin (HS) and low spin (LS) states. Here, only the simplest elastic interactions between adjacent molecules are considered and the system is exposed to the external pressure within the framework of $NPT$-Monte Carlo method. As a certain amount of pressure is applied, the first order thermal transition between uniform HS and LS phases transforms to a two-step transition with an emergent intermediate spin (IS) phase, where the HS and LS molecules are paired face to face between layers and form diagonally striped clusters within the layer. The difference in the size of HS and LS molecules is reflected both in the elastic interactions and in the enthalpy, and the IS phase could gain the latter over the loss of the former by significantly reducing its volume. The present pressure effect is interpreted to the chemical one in double-layered transition metal materials, which actually reveals a variety of multistep spin crossover transitions relevant to our numerical result.

Shape effects on the cluster spreading process of spin-crossover compounds analyzed within an elastic model with Eden and Kawasaki dynamics

In this paper we study the growth properties of domains of low-spin molecules in a high-spin background in open-boundary elliptically shaped spin-crossover systems within the framework of a mechanoelastic model. The molecules are situated on a triangular lattice and are linked by springs, through which they interact. Elliptical shapes are chosen in order to allow an in-depth analysis of cluster shapes as a function of the local curvature at their starting point and the length of the interface between the two phases. In contrast to the case of rectangular and hexagonal shapes, where the clusters always start from corners, we find that for ellipses clusters nucleate from vertices, covertices, or any other site. We apply and compare two kinds of dynamics, Eden-like and Kawasaki, in order to determine the stable shape of the clusters and the most probable starting points. We show that the wetting angle for small clusters is somewhat higher than $\ensuremath{\pi}/2$ and approaches this value only for large clusters. The stability of clusters is analyzed by comparing the Gibbs free energy to the elastic energy in the system and is discussed as a function of the cluster size, curvature of the starting place, and temperature.

Femtosecond spin-state photo-switching dynamics in an FeIII spin crossover solid accompanied by coherent structural vibrations

Femtosecond optical spectroscopy reveals coherent structural trapping accompanying spin-state photoswitching in a FeIII spin-crossover material.

Modification of Molecular Spin Crossover in Ultrathin Films

Scanning tunneling microscopy and local conductance mapping show spin-state coexistence in bilayer films of Fe[(H2Bpz2)2bpy] on Au(111) that is independent of temperature between 131 and 300 K. This modification of bulk behavior is attributed in part to the unique packing constraints of the bilayer film that promote deviations from bulk behavior. The local density of states measured for different spin states shows that high-spin molecules have a smaller transport gap than low-spin molecules and are in agreement with density functional theory calculations.

Crystal‐Structure Studies of Mononuclear Iron(II) Complexes with Two‐Step Spin Crossover: [Fe{5‐NO2‐sal‐N(1,4,7,10)}] Revisited

AbstractIn the region of the spin transition of spin‐crossover (SCO) compounds there coexist molecules in both high‐spin (HS) and low‐spin (LS) states. In the case of two‐step spin transition, theoretical predictions and computer simulations have shown that HS and LS complex molecules should be ordered in the plateau region. Several examples that support this hypothesis are already presented in the literature. Herein, we discuss a mononuclear complex of iron(II) with two‐step spin transition in terms of long‐range ordering of HS and LS molecules. In such compounds, spin transition is associated with the formation of a superstructure. However, previous studies of the [Fe{5‐NO2‐sal‐N(1,4,7,10)}] [5‐NO2‐sal‐N(1,4,7,10) = 5‐nitrosalicylaldehyde–1,4,7,10‐tetraazadecane] coordination complex have not revealed the occurrence of the satellite reflections in the SCO plateau region as a typical sign of the formation of a superstructure. Re‐investigations of this complex by using strong X‐ray sources and a charge‐coupled device (CCD) camera show that satellite reflections appear in the plateau region. This is evidence that also in this case the superstructure is formed in the plateau region with long‐range ordering of the HS and LS molecules. The two‐step spin transition is connected to the change of the conformer and a dramatic change in the hydrogen‐bonding system.

Pressure and Temperature Spin Crossover Sensors with Optical Detection

Iron(II) spin crossover molecular materials are made of coordination centres switchable between two states by temperature, pressure or a visible light irradiation. The relevant macroscopic parameter which monitors the magnetic state of a given solid is the high-spin (HS) fraction denoted nHS, i.e., the relative population of HS molecules. Each spin crossover material is distinguished by a transition temperature T1/2 where 50% of active molecules have switched to the low-spin (LS) state. In strongly interacting systems, the thermal spin switching occurs abruptly at T1/2. Applying pressure induces a shift from HS to LS states, which is the direct consequence of the lower volume for the LS molecule. Each material has thus a well defined pressure value P1/2. In both cases the spin state change is easily detectable by optical means thanks to a thermo/piezochromic effect that is often encountered in these materials. In this contribution, we discuss potential use of spin crossover molecular materials as temperature and pressure sensors with optical detection. The ones presenting smooth transitions behaviour, which have not been seriously considered for any application, are spotlighted as potential sensors which should stimulate a large interest on this well investigated class of materials.

The photo-induced commensurate modulated structure in site-selective spin crossover complex trans-[Fe(abpt)2(NCS)2

The photo-induced superstructure of polymorph C of trans-[Fe(abpt)(2)(NCS)(2)] (abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole) is discovered as a commensurate modulated structure by single-crystal X-ray diffraction under irradiation. The crystal structure at 25 K before the photo-irradiation composed of two crystallographically independent iron molecules, one of which exhibits high spin (HS) state and the other at low spin (LS) state. Under green laser light (λ = 532 nm) irradiation, the LS molecule (Fe1) is found to be excited to a metastable HS state and gives rise to a commensurate tripled superstructure along the c axis. In addition, it is confirmed that this modulation persists until the HS → LS relaxation temperature beyond 52 K. Our structural findings suggest that the structural modulation and the site-selective LS → HS excitation are highly correlated.

Multi-phase spin crossover in Fe(ptz)6(BF4)2

Abstract Transition metal complexes present solid state phase transitions associated with a change of the spin state, low-spin at low temperature to high-spin at high temperature, often with a significant change of metal-ligand bond lengths. Elastic interactions between small low-spin molecules and large high-spin ones play an important role in the phase transition. Since the discovery of spin crossover phenomenon, the complex [Fe (ptz) 6 ](BF 4 ) 2 has successfully attracted the interest of scientists because of its complete spin conversion and of its sensitivity to light. This very rich phase multi-stability also offers a unique possibility to investigate carefully the spin crossover phenomena in diverse fundamental cases (coupled with a ferroelastic transition, after quenching, after irradiation, …), and in an unusual case where the metal ion lies on a high-symmetry site. On the basis of results obtained by neutron scattering under high pressure, we present here the (pressure–temperature) phase diagram of the complex [Fe (ptz) 6 ](BF 4 ) 2 , which appears as seriously more complex than expected from the earlier literature, with in particular at least two new phases, one corresponding to complexes in a high-spin state but stacked in low symmetry, the other arising from an unexpected reconstructive phase transition.

Mixed-Valence Tetra- and Hexanuclear Manganese Complexes from the Flexibility of Pyridine-Containing β-Diketone Ligands

The reactions of [Mn3O(O2CCCl3)6(H2O)3] with 1-phenyl-3-(2-pyridyl)propane-1,3-dione (HL(1)) and 1-(2-pyridly)-3-(p-tolyl)propane-1,3-dione (HL(2)) in CH2Cl2 afford the mixed-valence Mn(II)2Mn(III)2 tetranuclear complexes [Mn4O(O2CCCl3)6(L(1))2] (1) and [Mn4O(O2CCCl3)6L2(2)] (2), respectively. Similar reactions employing [Mn3O(O2CPh)6(H2O)(py)2] with HL(1) and HL(2) give the Mn(II)3Mn(III)3 hexanuclear complexes [Mn6O2(O2CPh)8(L(1))3] (3) and [Mn6O2(O2CPh)8L3(2)] (4), respectively. Complexes 1.2CH2Cl2, 2.2CH2Cl2.H2O, 3.1.5CH2Cl2.Et2O.H2O, and 4.2CH2Cl2 crystallize in the triclinic space group P1, monoclinic space group P2(1)/c, monoclinic space group P2 1/ n, and monoclinic space group P2(1)/n, respectively. Complexes 1 and 2 consist of a trapped-valence tetranuclear core of [Mn(II)2Mn(III)2(mu4-O)](8+), and complexes 3 and 4 represent a new structural type, possessing a [Mn(II)3Mn(III)3(mu4-O)2](11+) core. The magnetic data indicate that complexes 3 and 4 have a ground-state spin value of S = 7/2 with significant magnetoanisotropy as gauged by the D values of -0.51 cm (-1) and -0.46 cm (-1), respectively, and frequency-dependent out-of-phase signals in alternating current magnetic susceptibility studies indicate their superparamagnetic behavior. In contrast, complexes 1 and 2 are low-spin molecules with an S = 1 ground state. Single-molecule magnetism behavior confirmed for 3 the presence of sweep-rate and temperature-dependent hysteresis loops in single-crystal M versus H studies at temperatures down to 40 mK.

Structural investigation of the photoinduced spin transition in the three states molecular system [Fe(2-pic)3]Cl2EtOH

We present the detailed results of the investigation by x-ray diffraction of the photoinduced phase transition in the tris(α-picolylamine)iron(II) chloride–ethanol complex. This system undergoes a two-steps spin transition between a high spin state at room temperature and a low spin state at low temperature. The intermediate phase consists of stripes of high spin and low spin molecules. The x-ray diffraction data evidence the structural rearrangement at the molecular scale accompanying the photoinduced change of electronic state between the low-spin phase and the photo-steady high-spin one, which is similar to the stable one in the high temperature phase. The dynamical mechanism of the transformation is discussed with the observation of a domain nucleation process, associated with the coexistence of the stable and photoinduced phases.

Resonant photon absorption in the low spin molecule V15

Resonant photon absorption in the low spin molecule V15

Spin crossover in iron(II) tris(2-(2′-pyridyl)benzimidazole) complex monitored by variable temperature methods: synchrotron powder diffraction, DSC, IR spectra, Mössbauer spectra, and magnetic susceptibility

The thermal expansion of the spin crossover system [Fe(pybzim)3](ClO4)2 · H2O (pybzim=2-(2′-pyridyl)benzimidazole) has been determined from powder X-ray data between 50 and 250 K; the wavelength of the synchrotron source was 1.21888(1) Å. The unit cell parameters of the triclinic crystal system were a=12.091 Å, b=12.225 Å, c=14.083 Å, α=77.70°, β=80.35°, γ=74.35°, and V=1944.9 Å3 at 250 K. In addition to the linear thermal expansion of the unit cell volume, an extra expansion due to the low-spin (LS) to high-spin (HS) transition is observed. The V(T) function shows a sudden increase comparable with the step in the effective magnetic moment at the transition region (140 K). A similar behavior is obtained on the basis of the infrared spectra. The absorption bands corresponding to the metal–ligand stretching modes change their intensities upon heating: the bands corresponding to the low-spin molecules (at ca. 409, 430, 443, and 460 cm−1) disappear in the gain of the high-spin bands (at 259 and 285 cm−1). The variable-temperature data obtained by different techniques (powder diffraction, EXAFS, IR spectra, Mössbauer spectra, magnetic susceptibility, DSC) have been transformed to a common basis – the temperature dependence of the high-spin mole fraction xHS(T). The application of the Ising-like (two-level) model of the spin crossover led to the thermodynamic data ΔH=2.6 kJ mol−1 and ΔS=19 J K−1 mol−1 as well as to the cooperativeness J/k≈110 K (subtracted from the susceptibility data) that characterizes the abruptness of the spin crossover in the solid state.

On the richness of supra-molecular chemistry and its openings in physics

Some branches of molecular and supra-molecular chemistry deal with magnetic ions (mainly of the 3d transition series). This leads to the subject of molecular magnetism. When magnetic molecules are sufficiently separated from each other to avoid inter-molecular exchange interactions, they form networks of spin-clusters, sometimes called ‘single molecule magnets’. However, this label can only apply to high-spin molecules, with high classical energy barriers. This paper gives a short presentation of the results obtained on the low-spin molecule V15, in collaboration with the Bielefeld group of Achim Müller.

Single-molecule magnets: a new family of Mn(12) clusters of formula [Mn(12)O(8)X(4)(O(2)CPh)(8)L(6)

The reaction of (NBu(n)(4))[Mn(8)O(6)Cl(6)(O(2)CPh)(7)(H(2)O)(2)] (1) with 2-(hydroxymethyl)pyridine (hmpH) or 2-(hydroxyethyl)pyridine (hepH) gives the Mn(II)(2)Mn(III)(10) title compounds [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hmp)(6)] (2) and [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hep)(6)] (3), respectively, with X = Cl. Subsequent reaction of 3 with HBr affords the Br(-) analogue [Mn(12)O(8)Br(4)(O(2)CPh)(8)(hep)(6)] (4). Complexes 2.2Et(2)O.4CH(2)Cl(2), 3.7CH(2)Cl(2), and 4.2Et(2)O.1.4CH(2)Cl(2) crystallize in the triclinic space group P1, monoclinic space group C2/c, and tetragonal space group I4(1)/a, respectively. Complexes 2 and 3 represent a new structural type, possessing isomeric [Mn(III)(10)Mn(II)(2)O(16)Cl(2)] cores but with differing peripheral ligation. Complex 4 is essentially isostructural with 3. A magnetochemical investigation of complex 2 reveals an S = 6 or 7 ground state and frequency-dependent out-of-phase signals in ac susceptibility studies that establish it as a new class of single-molecule magnet. These signals occur at temperatures higher than those observed for all previously reported single-molecule magnets that are not derived from [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(x)]. A detailed investigation of forms of complex 2 with different solvation levels reveals that the magnetic properties of 2 are extremely sensitive to the latter, emphasizing the importance to the single-molecule magnet properties of interstitial solvent molecules in the samples. In contrast, complexes 3 and 4 are low-spin molecules with an S = 0 ground state.

A new class of single-molecule magnets: mixed-valent [Mn12O8Cl4(O2CPh)8(hmp)6

The reaction of (NBun4)[Mn8O6Cl6(O 2CPh)7(H2O)2] with 2-(hydroxymethyl)pyridine (hmpH) or 2-(hydroxyethyl)pyridine (hepH) gives the MnII2MnIII10 complexes [Mn12O8- Cl4(O2CPh)8(hxp)6] [hxp− = hmp− (1) or hep− (2)]; these compounds are core isomers with markedly different magnetic properties, compound 1 having an S = 7 ground state and displaying strong out-of-phase ac susceptibility signals that establish it as a new class of single-molecule magnet, whereas compound 2 is a low-spin molecule with an S = 0 ground state.

Thermal and Light-Induced Spin Transition in the High- and Low-Temperature Structure of [Fe(0.35)Ni(0.65)(mtz)(6)](ClO(4))(2).

The thermal and light induced spin transition in [Fe(0.35)Ni(0.65)(mtz)(6)](ClO(4))(2) (mtz = 1-methyl-1H-tetrazole) was studied by (57)Fe Mössbauer spectroscopy and magnetic susceptibility measurements. In addition to the spin transition of the iron(II) complexes the compound undergoes a structural phase transition. The high-temperature structure could be determined by X-ray crystallography of the isomorphous [Fe(0.25)Ni(0.75)(mtz)(6)](ClO(4))(2) complex at room temperature. The X-ray structural analysis shows this complex to be rhombohedric, space group R&thremacr;, with a = 10.865(2) Å and c = 23.65(1) Å with three molecules in the unit cell. The transition to the low-temperature structure occurs at approximately 60 K without changing the spin state of the molecules. By subsequent heating of the complex the high-temperature structure is reached again between ca. 170 and 200 K. The spin transition behavior is strongly influenced by the structural changes, and the observed spin transition curves are completely different for the high- and low-temperature phases. In the high-temperature structure a complete and gradual spin transition between 220 and 120 K (T(1/2)(gamma(HS) = 0.5) = 185 K) is detected; the high-spin (HS) state is represented by one HS doublet in the Mössbauer spectra. In the low-temperature structure a two-step transition curve is detected in the heating mode. About 36% of the molecules show a LS (low-spin) --> HS transition between ca 50 and 75 K. Then the HS fraction stays constant up to 150 K. A further increase in the high-spin fraction is observed at temperatures above 150 K. In this structural phase the HS state is represented by two different HS doublets in the Mössbauer spectra. The formation of metastable HS states by making use of the LIESST effect is only possible in the low-temperature structure. By excitation of the LS molecules with green light, two different HS states are populated which show very different relaxation behavior. One HS state shows a relaxation to the LS state even at 10 K; the other HS state shows a very slow HS --> LS relaxation at 60 K (within days), leading to the HS fraction corresponding to the thermal equilibrium value.