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Density functional theory (DFT) methods are used for studying the variation in the orientation of the NO ligand in solid state [Fe(porphine)(NO)(1-MeIm)] systems. NO orientations are mapped by calculating the potential energy differences for all possible orientations of the nitrosyl nitrogen atom in the bent FeNO systems.

The low-frequency mode activity of metalloporphyrins is analyzed for iron porphine-halides and nitrophorin 4 (NP4) by using femtosecond coherence spectroscopy (FCS) in combination with polarized resonance Raman spectroscopy and density functional theory (DFT). The results have shown the potential of FCS as a sensitive probe of dynamic and functionally important nonplanar heme vibrational excitations that are induced by the protein environmental forces or by the chemical reactions in the aqueous phase.

The experimental and computational studies are carried out to obtain more direct vibrational signatures for protonation of the monooxygen ligand. The results establish the high sensitivity of the Fe-O stretching frequency and FeO tilting which would provide vibrational signatures for the protonation state in structural studies of ferryl heme protein intermediates.

The two polymorphs of six-coordinate [Fe(TpFPP)(1-Melm)(NO)] are used to study the interplay of structural changes and vibrational dynamics. The results have shown the distinct differences of CO versus NO heme complexes.

Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm-1. Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-NIm vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape). [ABSTRACT FROM AUTHOR]

Orientational disorder of the distal nitrosyl (NO) ligand in iron porphyrinates is a common phenomenon. We present an analysis of multitemperature crystallographic data for the order/disorder phenomenon. The observed temperature-dependent order/disorder and variable rotational orientations of nitrosyl ligands for six different six-coordinate iron porphyrinates have been examined in terms of the nonbonded contacts found in the solid state. Favorable orientations for NO can be identified either by calculation of the close nonbonded contacts or by evaluation of the geometry-dependent potential energy using semiempirical nonbonded potential functions. The nonbonded contacts display temperature-dependent differences consistent with observed structural differences. The motion of NO appears to be controlled by intermolecular interactions that allow a limited set of orientations, and under some conditions, only a single NO orientation is allowed. In some cases, the equilibria involving the orientations of NO can be analyzed using the van't Hoff relationship, and the free energy and enthalpy of the solid-state transitions can be evaluated. The intrinsic barriers to rotation of the NO were examined using a fine-meshed series of DFT calculations. The calculations also showed the detailed effects of the variation of the NO orientation on the equatorial bond distances. [ABSTRACT FROM AUTHOR]

The article reports on the study on the effects of the ligand orientation and bond distance in the modulation of iron dynamics in six-coordinate [Fe-(Porph)(1-MeIm)(NO)]3 derivatives. It is indicated that two crystalline polymorphs of [Fe(TρFPP)(1-MeIm)(NO)] that exhibit varying room temperature solid-state processes. Results show that the polymorphs allow the discovery of the interplay of structural changes and vibrational dynamics.

The effects of the deprotonation of coordinated imidazole on the vibrational dynamics of five-coordinate high-spin iron(II) porphyrinates have been investigated using nuclear resonance vibrational spectroscopy. Two complexes have been studied in detail with both powder and oriented single-crystal measurements. Changes in the vibrational spectra are clearly related to structural differences in the molecular structures that occur when imidazole is deprotonated. Most modes involving the simultaneous motion of iron and imidazolate are unresolved, but the one mode that is resolved is found at higher frequency in the imidazolates. These out-of-plane results are in accord with earlier resonance Raman studies of heme proteins. We also show the imidazole vs imidazolate differences in the in-plane vibrations that are not accessible to resonance Raman studies. The in-plane vibrations are at lower frequency in the imidazolate derivatives; the doming mode shifts are inconclusive. The stiffness, an experimentally determined force constant that averages the vibrational details to quantify the nearest-neighbor interactions, confirms that deprotonation inverts the relative strengths of axial and equatorial coordination.

The low-frequency vibrational characterization of the spin-crossover complex, five-coordinate cyano(tetraphenylporphyrinato)iron(II), [Fe(TPP)(CN)](-), is reported. Nuclear resonance vibrational spectroscopy has been used to measure all low-frequency vibrations involving iron at several temperatures; this yields vibrational spectra of both the low- (S = 0) and high-spin (S = 2) states. Multitemperature oriented single-crystal measurements facilitate assignments of the vibrational character of all modes and are consistent with the DFT-predicted spectra. The availability of the entire iron vibrational spectrum allows for the complete correlation of the modes between the two spin states. These data demonstrate that not only do the frequencies of the vibrations shift to lower values for the high-spin species as would be expected owing to the weaker bonds in the high-spin state, but also the mixing of iron modes with ligand modes changes substantially. Diagrams illustrating the changing character of the modes and their correlation are given. The reduced iron-ligand frequencies are the primary factor in the entropic stabilization of the high-spin state responsible for the spin crossover.

Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm(-1). Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-N(Im) vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape).