Search results for "SPIN STATES"

Pairing energy effects in cyanide complexes of CpCrIII

1999

International audience; The steric and electronic factors responsible for the reactivity differences between CN and Cl complexes of CpCrIII were examined by DFT/B3LYP computational techniques. The energy difference between quadruplet and doublet [CpCr(CN)2(PH3)], ΔED–Q, was calculated to be 21.2 kcal mol−1 with the LanL2DZ basis set. Although the high-spin configuration is still the ground state for the cyanide complex, the energy gap is 8.7 kcal mol−1 less than that found for the corresponding chloride species. The difference between quadruplet [CpCr(CN)2(PH3)] and doublet [CpCr(CN)2(PH3)2] less free PH3, ΔECr–P, is also smaller than for the Cl system. The components of ΔECr–P for CN and C…

Chiral spin crossover nanoparticles and gels with switchable circular dichroism

2015

Spin crossover complexes represent spectacular examples of molecular switchable materials. We describe a new approach towards homochiral coordination nanoparticles of [Fe(NH2trz)3](L-CSA)2 (NH2trz = 4-amino-1,2,4-triazole, L-CSA = L-camphorsulfonate) that display an abrupt switch of chiral properties associated with a cooperative spin transition. This is an original method that generates stable and additive-free colloidal solutions of nanoparticles with a spin transition around room temperature. The introduction of a chiral anion to the coordination framework makes these nanoparticles display specific chiro-optical (circular dichroism) properties that are different in high and low spin stat…

Light Induced Excited Pair Spin State in an Iron(II) Binuclear Spin-Crossover Compound

1999

Different Look at the Spin State ofCo3+Ions in aCoO5Pyramidal Coordination

2004

Using soft-x-ray absorption spectroscopy at the Co ${L}_{2,3}$ and O $K$ edges, we demonstrate that the ${\mathrm{Co}}^{3+}$ ions with the ${\mathrm{CoO}}_{5}$ pyramidal coordination in the layered ${\mathrm{Sr}}_{2}{\mathrm{CoO}}_{3}\mathrm{Cl}$ compound are unambiguously in the high spin state. Our result questions the reliability of the spin state assignments made so far for the recently synthesized layered cobalt perovskites and calls for a reexamination of the modeling for the complex and fascinating properties of these new materials.

High-spin states in tetrahedral X4 clusters (X = H, Li, Na, K)

2010

The high-spin electronic states for lithium, sodium, and potassium four-atom clusters were studied. In particular, we performed coupled cluster geometry optimization of the quintet state in tetrahedral geometry. The quintet state of these systems is characterized by having all the valence electron Unpaired, giving rise to the so-called no-pair bonding. Single-point full configuration interaction computations on the equilibrium geometries for the various Clusters are also presented. The analysis of the valence orbitals in a localized representation confirms the importance of the p atomic orbitals to explain this unusual type of bond. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 110: 8…

Temperature and pressure effects on the spin state of ferric ions in the [Fe(sal2-trien)][Ni(dmit)2] spin crossover complex

2008

Abstract Thermal and pressure effects have been investigated on the [Fe(sal 2 -trien)][Ni(dmit) 2 ] spin crossover complex by means of Mossbauer spectroscopic, calorimetric, X-ray diffraction and magnetic susceptibility measurements. The complex displays a complete thermal spin transition between the S = 5 2 and S = 1 2 spin states of Fe III near 245 K with a hysteresis loop of ca. 30 K. This transition is characterised by a change of the enthalpy, Δ H HL =7 kJ/mol, entropy, Δ S HL =29 J/Kmol, and the unit cell volume, Δ V HL =15.4 A 3 . Under hydrostatic pressures up to 5.7 kbar the thermal transition shifts to higher temperatures by ca. 16 K/kbar. Interestingly, at a low applied pressure …

Modelling of two step high spin⇌low spin transitions using the cluster variation method

1998

Abstract A thermodynamic description of high spin (HS)⇌low spin (LS) transition curves beyond the Bragg–Williams approximation is given using the Kikuchi cluster variation method (CVM). Transition curves of unusual behaviour (i.e. two step transition) are reproduced by short range interaction energies which are present in addition to long range elastic interaction between the spin changing molecules. The correlations in the distribution of the spin changing centers can be expressed analytically. They give rise to a reduced mixing entropy which was found experimentally in compounds with two step transitions.

Vibrational properties of 1D- and 3D polynuclear spin crossover Fe(II) urea-triazoles polymer chains and quantification of intrachain cooperativity

2020

Abstract The vibrational dynamics of the iron centres in 1D and 3D spin crossover Fe(II) 4-alkyl-urea triazole chains have been investigated by synchrotron based nuclear inelastic scattering. For the 1D system, the partial density of phonon states has been modelled with density functional theory methods. Furthermore, spin dependent iron ligand distances and vibrational modes were obtained. The previously introduced intramolecular cooperativity parameter H coop (Rackwitz et al, Phys. Chem. Chem. Phys. 2013, 15, 15450) has been determined to −31 kJ mol−1 for [Fe(n-Prtrzu)3(tosylate)2] and to +27 kJ mol−1 for [Fe(n-Prtrzu)3(BF4)2]. The change of sign in H coop is in line with the incomplete an…

Interplay between spin-crossover and luminescence in a multifunctional single crystal iron( ii ) complex: towards a new generation of molecular senso…

2019

Multifunctional mononuclear iron( ) complex coordinated with six phosphorescent ligands exhibiting correlated spin-crossover transition and enhanced fluorescence.

Photomagnetic properties of an Iron(II) low-spin complex with an unusually long-lived metastable LIESST state

2007

A comprehensive study of the photomagnetic behavior of the [Fe(L222N5)(CN)2].H2O complex has been carried out. This complex is characterized by a low-spin (LS) iron(II)-metal center up to 400 K and exhibits at 10 K the well-known Light-Induced Excited Spin State Trapping (LIESST) effect. The critical LIESST temperature (T(LIESST)) has been measured to be 105 K. The kinetics of the transition from the metastable high-spin (HS) state to the low-spin state have been determined and used for reproducing the experimental T(LIESST) curve. This study represents a second example of a fully low-spin iron(II)-metal complex up to 400 K, which can be photoexcited at low temperature with an atypical long…