Electronic states spin crossover

There will exist an equilibrium between the two states. If the ener between the two states, E, is of the order of kT, then the relative populations of the two states will vary with the temperature of the sample. In the Fe(III) dithiocarbamate series of complexes, [FeCRiRgdtcla], AE can be varied by suitable choice of substituents Ri and Rj. Although these are well removed from the FeSg molecular core, they can appreciably affect the electronic parameters of the central iron atom and of the surrounding crystal field of the sulfur atom by way of the conjugated system of the ligand (237). The results of the spin crossover are reflected in magnetic susceptibility data. 

Zarembowitch (1992) Electronic spin crossovers in solid state molecular compounds—some new aspects concerning cobalt(II) complexes [232]. 

Figure 9.29 Photo-induced spin crossover in transition metal ions (a) incident photons can successively promote electrons from the ground t2g state to the high-energy eg state and (b) spin crossover involving election transfer and excitation in KFeCo(CN)6-...

Nitroxides are the most common of the oxygen-centred biradicals to be reported. As a model for spin-crossover molecules, the nitronyl nitroxide (105) was prepared and by oxidation with PbC>2 afforded the triplet biradical (106) which was characterized by ESR (Scheme 15).242 The one-electron oxidation of (105) afforded the singlet cation (107) which was seen to exist in equilibrium with (106) in solution. The authors claim that pH-controlled interconversion between two species of different spin multiplicities in this way may provide die basis for novel magnetic switches or pH sensors. The N.N-dialkylamino nitronyl nitroxides (108) were prepared and afforded die diplet-state biradical cation species by one-electron oxidation with iodine.243 The authors propose that, by the similarity of die electronic structures, diese structures can be regarded as hetero-analogues of trimethylenemethane. A paper confirms die conversion of 3,3-dimethyldioxetane into die corresponding ring-opened 1,2-diol but refutes the... 

The electronic ground state that a particular metal center adopts is a function of the chromophore. In many cases the ground state may be derived from chemical knowledge (e. g., octahedral cobalt(HI) ( Aig) or tetrahedral Ni(II) (3T() complexes). However, based on the molecular mechanics formalism alone, this problem cannot be solved in a general way. Let us consider coordination compounds which are close to the spin-crossover limit (for example hexacoordinate iron(II) (1Aig/5T2g)). In these cases it is not possible to assign the atom type of the metal center without further information (experimental or theoretical). Therefore, molecular mechanics alone is not always able to predict the structural properties. 

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