Evidence of four light-induced metastable states in iron-nitrosyl complexes

Schaniel, Dominik; Woike, Th.; Tsankov, L.; Imlau, Mirco

doi:10.1016/j.tca.2004.11.024

Cited by 22 publications

(17 citation statements)

References 28 publications

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“…To adequately compare energies referring to two substances (our MNIC andS NP), we used numbersf rom DFT calculations in both cases.E xperimental values for the energies of the PL isomersa sw ell as activation energies are available for SNP and are usually substantially smallert han the calculatedo nes. [41] The population of the isonitrosyl (MS1) state in solid A[FeCl 3…”

Section: Computational Analysis Of the Mnic Uv/vis Spectramentioning

confidence: 99%

{FeNO}⁷‐Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

In‐Iam

Wolf

Wilfer

et al. 2018

Chemistry A European J

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Mononitrosyl-iron compounds (MNICs) of the Enemark-Feltham {FeNO} 7 type can be divided into ad oublet (S = 1/2) and aq uartet (S = 3/2) spin variant. The latter relies on weak-field co-ligands such as amine carboxylates. Aquaonly co-ligation appears to exist in the long-known "brownring" [Fe(H 2 O) 5 (NO)] 2 + cation, whichw as preparedo riginally from ferrous salts and NO in sulfuric acid. Ac hloride variant of this species, the green [FeCl 3 (NO)] À ion, was first prepared analoguosly by using hydrochloric instead of sulfuric acid. As at etrahedral species, it is the simple prototypeo fs ulfurbonded {FeNO} 7 (S = 3/2) MNICs of biological significance. Although it has been investigated form ore than ac entury, neitherc lean preparative routes nor reliable structuralp arameters were available for the [FeCl 3 (NO)] À ion and related speciess uch as the [FeCl 2 (NO) 2 ] À ion, ap rototypical dinitrosylirons pecies( a" DNIC"). In this work, both issues have been resolved. In addition, we report on ac omputational study on the ground-and excited-state properties including an assignment of the chromophoric transitions. Photoinduced metastable isomersw ere characterisedi nacombined experimental and computational approacht hat resulted in the confirmation of as ingle photoinduced linkage isomer of the paramagnetic nitrosyl-metal coordination entity.

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Section: Computational Analysis Of the Mnic Uv/vis Spectramentioning

confidence: 99%

{FeNO}⁷‐Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

In‐Iam

Wolf

Wilfer

et al. 2018

Chemistry A European J

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“…The structures of GS and of the metastable states MS1 and MS2 are known from X ray and neutron diffraction measurements at low temperatures in the static regime [19 21]. The lifetime of both states below 200 and 150 K, respectively, is nearly infinite due to the activation energies of 0.68 eV (MS1) and 0.43 eV (MS2) [22]. Both metastable states are lying about 1 eV above the ground state (see Figure 1) [23].…”

Section: Introductionmentioning

confidence: 99%

Unraveling the mechanism of NO ligand photoisomerism by time-resolved infrared spectroscopy

Gallé

Nicoul

Woike

et al. 2012

Chemical Physics Letters

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UV Vis and infrared femtosecond spectroscopy makes it possible to reveal all different steps of photochemical reactions after the electronic excitation. The electronic relaxations are observed in the UV Vis spectral range whereas the nuclear motions are monitored in the infrared spectral range. We used femtosecond time resolved infrared spectroscopy to demonstrate the photoisomerization of the NO ligand photoinduced by a visible femtosecond pulse in a Na 2 [Fe(CN) 5 NO]Á2H 2 O single crystal occurs in about 350 fs. The analysis of data makes it possible to unravel the mechanism leading to the photoiso merization of the NO ligand.

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“…It is difficult to say if this new minimum is related to NO linkage photoisomerization. The detection of this minimum is hardly surprising, since up to date the question about the number of metastable states, which can be accessed by light-illumination, has not been answered conclusively [47]. The answer to this question requires thorough analysis and a significant amount of computationally expensive calculations, which reach far beyond the scope of the present work.…”

Section: Influence Of the Environmentmentioning

confidence: 82%

DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes

Сизова¹,

Lubimova²,

Sizov³

et al. 2008

Zeitschrift Für Kristallographie - Crystalline Materials

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The linkage isomers of the [M(NO)(CN) 5 ] 2-(M ¼ Fe, Ru, Os), [Ru(NO)Cl 5 ] 2-, trans-[Ru(NO)(NH 3 ) 4 (L)] qþ (L ¼ NH 3 , H 2 O, nicotinamide, imidazole, pyridine, pyrazine, NO 2 -, OH -, Cl -), and trans-[Ru(NO)L 4 (OH)] q (L ¼ pyridine, NO 2 -) ions are studied by density functional theory. DFT calculations show that the electronic ground-state potential surface of these nitrosyl complexes has the local minima corresponding to h 2 -NO and h 1 -O linkage isomers, of which the former is characterized by lower energy. The stationary points on the ground state potential energy surface along the GS ! MS2 ! MS1 path for the [M(NO)(CN) 5 ] 2-(M ¼ Fe, Ru, Os) and [Ru(NO)Cl 5 ] 2-complexes were found. The calculations of infrared spectra of linkage isomers [Ru(NO)Cl 5 ] 2-and [Ru(NO)(CN) 5 ] 2-are carried out. The analysis of quantum chemical bond orders indicates a noticeable delocalization of p-electron density along the L trans --M--NO axis and a possibility of direct interactions between NO and equatorial ligands in the structures with the bent {MNO} group.

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Evidence of four light-induced metastable states in iron-nitrosyl complexes

Cited by 22 publications

References 28 publications

{FeNO}⁷‐Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

{FeNO}⁷‐Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

Unraveling the mechanism of NO ligand photoisomerism by time-resolved infrared spectroscopy

DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes

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Evidence of four light-induced metastable states in iron-nitrosyl complexes

Cited by 22 publications

References 28 publications

{FeNO}7‐Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

{FeNO}7‐Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

Unraveling the mechanism of NO ligand photoisomerism by time-resolved infrared spectroscopy

DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes

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{FeNO}⁷‐Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

{FeNO}⁷‐Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism