Investigation of the Mossbauer Effect in Tin Compounds

Gol’danskii, R. I.; Gorodinskii, G. M.; Korytko, L. A.; Krizhanskii, L.M.; Makarov, E. F.; Suzdalev, I. P.; Khrapov, V. V.

doi:10.1007/978-1-4899-4848-9_23

Cited by 3 publications

(4 citation statements)

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“…The resilience determines the temperature dependence of the recoilless fraction in Mossbauer spectroscopy, 48 and the anisotropy thus suggests that measurable intensity asymmetry could be observable in the Mossbauer quadrupole doublet at sufficiently high temperatures, a phenomenon known as the Goldanskii-Karyagin effect. 49,50 Previously we have reported temperature-dependent NRVS studies on the five-coordinate cyano iron(II) [Fe(TPP)-(CN)] − , which shows thermally induced S = 0 ⇋ S = 2 spin crossover and has a low spin state below 150 K. 51,52 The DFT calculations on the low spin state predicted highly pure vibrations in three orthogonal directions with x and y aligned along the Fe−N p bonds (4N), 51 contrasted to the current case, where x and y are aligned along the four C meso carbon atoms (4C). This remarkably different in-plane vibrational coordinates has led to studies on the electronic structures of these carbon donor ligands (:CR = CCl 2 , CN − , and CO), and comparisons of the frontier orbital interactions between iron d orbitals and ligand π* orbitals are given in Figures 7, S9 , where the d π orbitals are parallel or perpendicular to the ligand plane FeNO (4C), 6,36,53,54 and in-plane anisotropy in the same orientations has been observed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Moreover, the values in Table are the first characterization of anisotropy in the resilience. The resilience determines the temperature dependence of the recoilless fraction in Mössbauer spectroscopy, and the anisotropy thus suggests that measurable intensity asymmetry could be observable in the Mössbauer quadrupole doublet at sufficiently high temperatures, a phenomenon known as the Goldanskii-Karyagin effect. , …”

Section: Results and Discussionmentioning

confidence: 99%

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How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN^–) Analogues in the Axial Bond?

et al. 2018

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Compared to well studied diatomic ligands (NO, CN, CO), the axial bonds of carbene hemes is much less known although its significance in biological chemistry. The unusually large quadrupole splitting (Δ E = +2.2 mm·s) and asymmetric parameter (η = 0.9) of the five-coordinate heme carbene [Fe(TTP)(CCl)], which is the largest among all known low spin ferrohemes, has driven investigations by means of Mössbauer effect Nuclear Resonance Vibrational Spectroscopy (NRVS). Three distinct measurements on one single crystal (two in-plane and one out-of-plane) have demonstrated comprehensive vibrational structures including stretch (429) and bending modes (472 cm) of the axial Fe-CCl, and revealed iron vibrational anisotropy in three orthogonal directions for the first time. Frontier orbital analysis especially comparisons with diatomic analogues (NO, CN, CO) suggest that CCl, similar to NO, has led to strong but anisotropic π bonding in a ligand-based "4C"-coordinate which induced the vibrational anisotropies and very large Mössbauer parameters. This is contrasted to CN and CO complexes which possess a porphyrin-based "4N"-coordinate electronic and vibrational structures due to inherent on-axis linear ligation.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN^–) Analogues in the Axial Bond?

et al. 2018

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“…Finally, it is worth noting that in none of these compounds can a vibrational anisotropy (Gol'danskii−Karyagin effect) be extracted from the temperature-dependent spectroscopic data, even though the ring planes are (nearly) coplanar, and a 5-fold symmetry axis perpendicular to these planes passes through the metal centers. As a result of the random orientation of the sample in the spectrometer, no significant temperature-independent intensity asymmetry is observed.…”

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confidence: 99%

Bonding, Hyperfine Interactions, and Lattice Dynamics of Cationic and Neutral Ferrocenyl-Substituted Allylic and Cumulenic Compounds

et al. 1997

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The synthesis and spectroscopic characterization (by mass, UV-visible, IR, NMR and (57)Fe Mössbauer spectroscopy) of three new compounds related to seven recently published ferrocenyl-substituted allylic and cumulenic compounds are reported and have made it possible to effect a systematic evaluation of the parameters extractable from temperature-dependent gamma ray resonance studies. For the neutral species, the hyperfine parameters (IS and QS) of the sigma-bonded ferrocenyl groups are insensitive to the structural details of the allylic or cumulenic carbon framework. The temperature dependence of the recoil-free fraction is dominated by the Cp ring-iron atom interaction, and is not diagnostic of the detailed molecular architecture. In the case of the carbocationic complexes, two distinct iron sites are resolvable from the Mössbauer data. The detailed temperature-dependent behavior of the hyperfine parameters and recoil-free fraction for 10 complexes with either equivalent termini, linked by similar, but different types of bridges (neutral 1-5), or with inequivalent moieties linked by related or identical connectors (cationic 6-10), has been elucidated over the temperature range 90

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“…It has been well established since the seminal work of Gol'danskii and Karyagin that temperature-dependent Mössbauer spectroscopy (MS) can elucidate the details of the motional anisotropy of the MS active atom by transmission scattering experiments. These early ideas were applied to organotin complexes in a series of studies, including those in which the metal atom was expected to evidence a large difference in the mean-square amplitude of vibration parallel and perpendicular to the highest local symmetry axis.…”

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The Unexpected Motional Isotropy of the Tin Atom in a Tricoordinate Stannylium Cation

et al. 2003

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The dynamics of the metal atom in the recently isolated tricoordinate tin complex tris(2,4,6-triisopropylphenyl)stannylium tetrakis(pentafluorophenyl)borate was examined by temperature-dependent (119)Sn Mössbauer spectroscopy over the temperature range 90 K < T < 170 K. Contrary to expectation, the metal atom motion in this temperature range is isotropic within experimental error of the Mössbauer data, and is only moderately anisotropic, even at 293 K, as evidenced by single crystal X-ray diffraction data. The hyperfine parameters at 90 K are completely consistent with trigonal coordination involving sp(2) hybridization of the 5s5p bonding orbitals of tin.

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Investigation of the Mossbauer Effect in Tin Compounds

Cited by 3 publications

References 2 publications

How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN^–) Analogues in the Axial Bond?

How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN^–) Analogues in the Axial Bond?

Bonding, Hyperfine Interactions, and Lattice Dynamics of Cationic and Neutral Ferrocenyl-Substituted Allylic and Cumulenic Compounds

The Unexpected Motional Isotropy of the Tin Atom in a Tricoordinate Stannylium Cation

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Investigation of the Mossbauer Effect in Tin Compounds

Cited by 3 publications

References 2 publications

How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN–) Analogues in the Axial Bond?

How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN–) Analogues in the Axial Bond?

Bonding, Hyperfine Interactions, and Lattice Dynamics of Cationic and Neutral Ferrocenyl-Substituted Allylic and Cumulenic Compounds

The Unexpected Motional Isotropy of the Tin Atom in a Tricoordinate Stannylium Cation

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How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN^–) Analogues in the Axial Bond?

How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN^–) Analogues in the Axial Bond?