Spin-state isomers

V LH > 10 s. For molecules which are not EPR silent, this limiting value may be better defined. In the case where the EPR spectra of both spin-state isomers are observed, the lifetime is determined by Tl = IAlh > 10 ° s. 

Such a short spin-equilibrium relaxation time raises the question of whether discrete spin state isomers exist. Their existence is affirmed by two observations. One is the persistence of electronic spectral bands typical of the low-spin 2E state over a wide temperature range in solid samples (98). The other is the observation of EPR signals characteristic of the 2E state in both solids and solutions between 4 and 293 K (98,139). At very low temperatures EPR signals of both spin states can be observed simultaneously (98). At low temperatures hyperfine splitting into eight lines is observed from coupling with the 1 = 7/2 Co nucleus. As the temperature is raised the spectral features broaden and the hyperfine resolution is lost. This implies a relaxation process on the EPR time scale of 1010 sec-1, or a relaxation time of the order 0.1 nsec, consistent with the upper limit set by the ultrasonic experiments. 

Parkin. G. Hoffmann, R. Bond-stretch isomers and spin-state isomers A comment on the article Bond-Stretch Isomers Fact not Fiction. Angew. Chem., Int. Ed. Engl. 1994. 33, 1462. 

Murillo. C.A. Wang, X. Tuning the metal-metal bonds in the linear tricobalt compound Co3(dpa)4Cl2 Bond-stretch and spin-state isomers. Inorg. Chem. 2001. 40. 1256-1264. 

The possibility is, however, ruled out since the g values of [Fe(0ETPP)(Hlm)2]CI04, g = 2.72, 2.37, and 1.64, determined under the same condition are quite different from those of the S = I /2 complex observed at 4 K. The EPR spectrum can best be explained in terms of the equilibrium among all the possible spin-state isomers of iron(lll) porphyrin complexes, that is, S= I/2, S = 3/2, and 5 = 5/2. Thus, the spin-crossover triangle shown in Fig. 10.20 has been completed in [Fe(OETPP)(Hlm)]+. 

Spin-state transitions have been studied by the application of numerous physical techniques such as the measurement of magnetic susceptibility, optical and vibrational spectroscopy, the Fe-Mbssbauer effect, EPR, NMR, and EXAFS spectroscopy, the measurement of heat capacity, and others. Most of these studies have been adequately reviewed. The somewhat older surveys [3, 19] cover the complete field of spin-state transitions. Several more recent review articles [20, 21, 22, 23, 24, 25] have been devoted exclusively to spin-state transitions in compounds of iron(II). Two reviews [26, 27] have considered inter alia the available theoretical models of spin-state transitions. Of particular interest is the determination of the X-ray crystal structures of spin transition compounds at two or more temperatures thus approaching the structures of the pure HS and LS electronic isomers. A recent survey [6] concentrates particularly on these studies. 

Spin-state equilibria between low-spin (LS Si) and high-spin (HS S2) electronic isomers in solution may be characterized by ... 

The description of states participating in a spin-state transition as electronic isomers with discrete nuclear configurations, in particular different metal-ligand distances, requires that separate electronic and vibrational spectra of the two spin states exist. Indeed, a superposition of the individual vibrational spectra of the two states is in general observed, the relative contribution of the states being a function of temperature [41, 139, 140, 141, 142]. This observation sets a lower limit for the spin-state lifetime longer than the nuclear vibrational period, i.e.,... 

The simultaneous observation of the two EPR spectra has been reported in particular for several tris(dithiocarbamato)iron(III) complexes [Fe(R2NC(S)S)3] where R = cyclohexyl [143], hydroxyethyl [144], and n-butyl [145, 146]. In addition, a considerable number of iron(III) complexes of the type [Fe" -N402] has been found which show EPR spectra of both the HS and LS isomers. These comprise [Fe(X-SalEen)2] Y2 where X-SalEen is the Schiff-base ligand obtained by condensation of X-substituted salicylaldehyde and IV-ethylethylenediamine [147] and similar compounds [100, 148, 149, 150, 151]. For the cobalt(II) complex [Co(terpy)2] (004)2, it is not completely clear whether the two observed EPR spectra are due to HS and LS states related by a spin-state transformation [152]. 

A unique situation is encountered if Fe-M6ssbauer spectroscopy is applied for the study of spin-state transitions in iron complexes. The half-life of the excited state of the Fe nucleus involved in the Mossbauer experiment is tj/2 = 0.977 X 10 s which is related to the decay constant k by tj/2 = ln2/fe. The lifetime t = l//c is therefore = 1.410 x 10 s which value is just at the centre of the range estimated for the spin-state lifetime Tl = I/Zclh- Thus both the situations discussed above are expected to appear under suitable conditions in the Mossbauer spectra. The quantity of importance is here the nuclear Larmor precession frequency co . If the spin-state lifetime Tl = 1/feLH is long relative to the nuclear precession time l/co , i.e. Tl > l/o) , individual and sharp resonance lines for the two spin states are observed. On the other hand, if the spin-state lifetime is short and thus < l/o) , averaged spectra with intermediate values of quadrupole splitting A q and isomer shift 5 are found. For the intermediate case where Tl 1/cl , broadened and asymmetric resonance lines are obtained. These may be the subject of a lineshape analysis that will eventually produce values of rate constants for the dynamic spin-state inter-conversion process. The rate constants extracted from the spectra will be necessarily of the order of 10 -10 s"F... 

Interesting is a comparison of the volumes occupied by individual complexes in solution and in the solid state. The partial molal volumes can be obtained from precise measurements of the solution densities of the complexes as a function of concentration [177]. These values may be subsequently compared with the unit cell volumes per complex molecule derived from the crystal structure. For Fe[HB(pz)3]2, the apparent molal volume in tetrahydrofuran solution was determined as 340.9 em mol Taking into account that the complex in solution forms an equilibrium between 86% LS and 14% HS isomers and employing the volume difference between the two spin states AF° = 23.6 cm mol S the volume of the LS isomer was calculated as 337.6 cm mol This value agrees closely with the volume of 337.3 cm mol for the completely LS complex in solid Fe[HB(pz)3]2 [105]. 

The studies show that the observed crystal volume is in fact composed of the fractional contributions from the unit cell volumes of the HS and LS isomers of the compound and a linear volume change with temperature as expressed in Eq. (128). Similarly, the observed lattice constants are formed from a deformation contribution proportional to the HS fraction and a contribution from thermal expansion following Eq. (131). This is a convincing demonstration that it is the internal variation of the molecular units occurring in the course of the spin-state transition which determines, at least in principle, the observed crystal properties. 

The spin state of the compounds XFe(R2dtc)2 is 3/2 (64). Mossbauer spectra of ClFe(Et2 tc)2 in solution are almost identical with the spectrum of the six-coordinated Fe(Et2magnetic susceptibility and in the isomer shift and quadrupole splitting parameters suggests a geometrical correspondency in solution, which can be attained by the binding of a solvent molecule to the sixth coordination site of the ClFe(Et2[Pg.98]

The recoil-free fraction depends on the oxidation state, the spin state, and the elastic bonds of the Mossbauer atom. Therefore, a temperature-dependent transition of the valence state, a spin transition, or a phase change of a particular compound or material may be easily detected as a change in the slope, a kink, or a step in the temperature dependence of In f T). However, in fits of experimental Mossbauer intensities, the values of 0 and Meff are often strongly covariant, as one may expect from a comparison of the traces shown in Fig. 2.5b. In this situation, valuable constraints can be obtained from corresponding fits of the temperature dependence of the second-order-Doppler shift of the Mossbauer spectra, which can be described by using a similar approach. The formalism is given in Sect. 4.2.3 on the temperature dependence of the isomer shift. 

The isomer shift is considered the key parameter for the assignment of oxidation states from Mossbauer data. The early studies, following the first observation of an isomer shift for Fe203 [7], revealed a general correlation with the (formal) oxidation state of iron. However, isomer shifts have also been found to depend on the spin state of the Mossbauer atom, the number of ligands, the cr-donor and the... 

Fig. 4.3 Ranges of isomer shifts observed for Fe compounds relative to metallic iron at room temperature (adapted from [24] and complemented with recent data). The high values above 1.4-2 mm s were obtained from Co emission experiments with insulators like NaCl, MgO or Ti02 [25-28], which yielded complex multi-component spectra. However, the assignment of subspectra for Fe(I) to Fe(III) in different spin states has never been confirmed by applied-field measurements, or other means. More recent examples of structurally characterized molecular Fe (I)-diketiminate and tris(phosphino)borate complexes with three-coordinate iron show values around 0.45-0.57 mm s [29-31]. The usual low-spin state for Fe(IV) with 3d configuration is 5 = 1 for quasi-octahedral or tetrahedral coordination. The low-low-spin state with S = 0 is found for distorted trigonal-prismatic sites with three strong ligands [30, 32]. Occurs only in ferrates. There is only one example of a molecular iron(VI) complex it is six-coordinate and has spin S = 0 [33]...

Table 5.4 Linear fit data for Fe Mossbauer isomer shift predictions using the linear equation 5 = h (p - c) + a. A collection of 21 iron complexes with varying charge, oxidation- and spin-states have been studied (taken from [11])...

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