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DFT calculations of the mononuclear Fe(II) spin crossover complexes [Fe(L)](2+) (L = ({bis[N-(2-pyridylmethyl)-3-aminopropyl](2-pyridylmethyl)amine})), ({[N-(2-pyridylmethyl)-3-aminopropyl][N-(2-pyridylmethyl)-2-aminoethyl](2-pyridylmethyl)amine}) and ({bis[N-(2-pyridylmethyl)-2-aminoethyl](2-pyridylmethyl)amine}) abbreviated as (66), (56) and (55) have been performed in order to explain the observed spin transition temperature differences. The complexes differ in the size of two chelate rings, revealing two six-membered, one six-membered and one five-membered, and two five membered rings for (66), (56) and (55), respectively. Calculations of the electronic energy differences ΔEel = Eel(HS) - Eel(LS) with the use of the basis set TZVP with B3LYP*, PBE, TPSS and TPSSh functionals reproduced the experimentally observed trends. The best reproduction of bond distances is obtained using the TPSSh functional. The Continuous Shape Measure (CShM) analysis of the optimised structures of all six spin isomers revealed the most significant distortion from the trigonal prism for the low-spin (66) system, which has the lowest spin transition temperature. The corresponding trigonal twist is proposed to be the main cause of releasing strain that is induced by the size of two fused chelate rings. Different conformers of low-spin and high-spin (66) systems were modelled using the TPSSh/TZVP method, including the calculations of transition states of conformational rearrangements in both spin isomers. A normal co-ordinate analysis was performed for all six spin isomers. This allows the assignment of previously reported Raman marker bands to specific modes of the (66) system. The estimate of the vibrational contribution to the spin transition entropy revealed values of 50-60 J K(-1) mol at room temperature for all three complexes.

The vibrational properties of the cationic spin crossover (SCO) coordination polymers [{Fe(4-amino-1,2,4-triazole)(3)}(+2)](n) containing the anions chlorine, methanosulfonate and 1-naphthalenesulfonate have been studied via nuclear inelastic scattering of synchrotron radiation (NIS) as well as by Raman spectroscopy. Although the different anions have a strong influence on the spin crossover temperature, they have little effect on the positions of the spin marker bands in the NIS and Raman spectra. By comparing the line positions of the NIS spin marker bands with those observed by Raman spectroscopy, it has been possible to distinguish vibrations symmetry (A(u) or A(g)) because modes of A(u) and A(g) symmetries are NIS active, but only the A(g) modes are Raman active. The normal mode analysis of charge compensated cationic pentameric and hexameric model structures which have been obtained by density functional calculations reproduces the experimentally observed mode frequencies and the geometry optimization reproduces iron-ligand distances reported for these and related SCO coordination complexes. The effect of charge compensation appears to be independent of the choice of the functional and the basis set which shows that DFT calculations using B3LYP in conjunction with the basis set CEP-31G are a time effective approach in order to study vibrational properties of Fe(II) SCO compounds.

The vibrational modes of the low-spin and high-spin isomers of the spin crossover complex [Fe(phen)(2)(NCS)(2)] (phen = 1,10-phenanthroline) have been measured by IR and Raman spectroscopy and by nuclear inelastic scattering. The vibrational frequencies and normal modes and the IR and Raman intensities have been calculated by density functional methods. The vibrational entropy difference between the two isomers, DeltaS(vib), which is--together with the electronic entropy difference DeltaS(el)--the driving force for the spin-transition, has been determined from the measured and from the calculated frequencies. The calculated difference (DeltaS(vib) = 57-70 J mol(-1) K(-1), depending on the method) is in qualitative agreement with experimental values (20-36 J mol(-1) K(-1)). Only the low energy vibrational modes (20% of the 147 modes of the free molecule) contribute to the entropy difference and about three quarters of the vibrational entropy difference are due to the 15 modes of the central FeN(6) octahedron.