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Title: Neutron diffraction shows a photoinduced isonitrosyl linkage isomer in the metastable state SI of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2D{sub 2}O

Abstract

We report neutron diffraction experiments on the light-induced metastable state SI in single crystals of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2D{sub 2}O. It is shown that the metastable state SI corresponds to a linkage isomer of the NO group, the so-called isonitrosyl configuration where the NO ligand is oxygen bound to the central iron atom.

Authors:
 [1];  [2];  [3];  [4];  [5]; ;  [6]
  1. Institut fuer Experimentalphysik, Universitaet Wien, Boltzmanngasse 5, A-1090 Wien (Austria)
  2. (Germany)
  3. Institut fuer Mineralogie und Geochemie, Universitaet zu Koeln, Zuelpicherstrasse 49b, D-50674 Koeln (Germany)
  4. Laboratory for Neutron Scattering, ETH Zuerich and Paul Scherrer Institute, 5232 Villigen, PSI (Switzerland)
  5. Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 18221 Praha 8 (Czech Republic)
  6. Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3000 Bern 9 (Switzerland)
Publication Date:
OSTI Identifier:
20788156
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. B, Condensed Matter and Materials Physics; Journal Volume: 73; Journal Issue: 17; Other Information: DOI: 10.1103/PhysRevB.73.174108; (c) 2006 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ATOMS; CYANIDES; IRON COMPOUNDS; ISOMERS; LIGANDS; METASTABLE STATES; MONOCRYSTALS; NEUTRON DIFFRACTION; NITRIC OXIDE; SODIUM COMPOUNDS; VISIBLE RADIATION

Citation Formats

Schaniel, D., Institut fuer Mineralogie und Geochemie, Universitaet zu Koeln, Zuelpicherstrasse 49b, D-50674 Koeln, Woike, Th., Schefer, J., Petricek, V., Kraemer, K. W., and Guedel, H. U. Neutron diffraction shows a photoinduced isonitrosyl linkage isomer in the metastable state SI of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2D{sub 2}O. United States: N. p., 2006. Web. doi:10.1103/PHYSREVB.73.1.
Schaniel, D., Institut fuer Mineralogie und Geochemie, Universitaet zu Koeln, Zuelpicherstrasse 49b, D-50674 Koeln, Woike, Th., Schefer, J., Petricek, V., Kraemer, K. W., & Guedel, H. U. Neutron diffraction shows a photoinduced isonitrosyl linkage isomer in the metastable state SI of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2D{sub 2}O. United States. doi:10.1103/PHYSREVB.73.1.
Schaniel, D., Institut fuer Mineralogie und Geochemie, Universitaet zu Koeln, Zuelpicherstrasse 49b, D-50674 Koeln, Woike, Th., Schefer, J., Petricek, V., Kraemer, K. W., and Guedel, H. U. Mon . "Neutron diffraction shows a photoinduced isonitrosyl linkage isomer in the metastable state SI of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2D{sub 2}O". United States. doi:10.1103/PHYSREVB.73.1.
@article{osti_20788156,
title = {Neutron diffraction shows a photoinduced isonitrosyl linkage isomer in the metastable state SI of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2D{sub 2}O},
author = {Schaniel, D. and Institut fuer Mineralogie und Geochemie, Universitaet zu Koeln, Zuelpicherstrasse 49b, D-50674 Koeln and Woike, Th. and Schefer, J. and Petricek, V. and Kraemer, K. W. and Guedel, H. U.},
abstractNote = {We report neutron diffraction experiments on the light-induced metastable state SI in single crystals of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2D{sub 2}O. It is shown that the metastable state SI corresponds to a linkage isomer of the NO group, the so-called isonitrosyl configuration where the NO ligand is oxygen bound to the central iron atom.},
doi = {10.1103/PHYSREVB.73.1},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 17,
volume = 73,
place = {United States},
year = {Mon May 01 00:00:00 EDT 2006},
month = {Mon May 01 00:00:00 EDT 2006}
}
  • The structure of the light-induced metastable state SII of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2H{sub 2}O was investigated by single-crystal neutron diffraction. The population of SII of 16(3)% was determined by an in situ transmission measurement. The final structural refinement yields a side-on bonded configuration of NO in the metastable state SII with distances Fe-O, Fe-N, and N-O of 2.01(5) A, 1.96(5) A, and 1.11(8) A, respectively. The angle Fe-N-O is 77(4) deg. The population determined from the refinement is 12(2)%, in good agreement with the value of 16(3)% determined from the independent in situ transmission measurement.
  • The magnetic properties and photoinduced magnetization of a Prussian blue analog, K{sub x}Co[Fe(Cn){sub 6}]{sub y}{center_dot}ZH{sub 2}O (x{approx}0.16, y{approx}0.72, z{approx}4.4) were systematically studied. The frequency dependence of the linear ac susceptibility, the irreversibility in the field-cooled/zero-field-cooled magnetization (M{sub FC}/M{sub ZFC}), and the relaxation of M{sub ZFC} suggest a cluster glass behavior. Illumination with red light leads to an increase in the magnetic irreversibility. While M{sub FC} is significantly increased after illumination, M{sub ZFC} at low temperatures is decreased. The observed photoinduced magnetic effects are explained within a cluster glass model. The photoinduced increase in the concentration of spins leads to amore » shift of dynamics toward longer length and time scales, resulting in freezing of spin clusters at a higher temperature. (c) 2000 American Institute of Physics.« less
  • The reaction of Re{sub 2}O{sub 7} with XeF{sub 6} in anhydrous HF provides a convenient route to high-purity ReO{sub 2}F{sub 3}. The fluoride acceptor and Lewis base properties of ReO{sub 2}F{sub 3} have been investigated leading to the formation of [M][ReO{sub 2}F{sub 4}] [M = Li, Na, Cs, N(CH{sub 3}){sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 2}F{sub 3}(CH{sub 3}CN). The ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and Re{sub 3}O{sub 6}F{sub 10{sup {minus}} anions and the ReO{sub 2}F{sub 3}(CH{sub 3}CN) adduct have been characterized in the solidmore » state by Raman spectroscopy, and the structures [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{approximately}3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN have been determined by X-ray crystallography. The structure of ReO{sub 2}F{sub 4}{sup {minus}} consists of a cis-dioxo arrangement of Re-O double bonds in which the Re-F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re{sub 2}O{sub 4}F{sub 7}{sup {minus}} and Re{sub 3}O{sub 6}F{sub 10}{sup {minus}} anions and polymeric ReO{sub 2}F{sub 3} are open chains containing fluorine-bridged ReO{sub 2}F{sub 4} units in which each pair of Re-O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re-F bonds trans to Re-O bonds as in ReO{sub 2}F{sub 4}{sup {minus}} and by the occurrence of both fluorine bridges trans to Re-O bonds. Fluorine-19 NMR spectra show that ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) have cis-dioxo arrangements in CH{sub 3}CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO{sub 2}F{sub 4}{sup {minus}} and ReO{sub 2}F{sub 3}(CH{sub 3}CN), where CH{sub 3}CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN was obtained by hydrolysis of ReO{sub 2}F{sub 3}(CH{sub 3}CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.« less
  • Co{sub 2}{l_brace}[N(CN){sub 2}]{sub 4}bpym{r_brace}{center_dot}H{sub 2}O (1) and M{l_brace}[N(CN){sub 2}]{sub 2}bpym{r_brace}{center_dot}H{sub 2}O [M = Mn (2a), Fe (2b), Co (2c); bpym = 2,2{prime}-bipyrimidine] have been synthesized and characterized structurally and magnetically. All of the compounds crystallize in the orthorhombic space group Pnma. The unit cell parameters for 1 are a = 16.1684(5) {angstrom}, b = 12.9860(3) {angstrom}, c = 10.4207(3) {angstrom}, and Z = 4. Compound 1 is a 2-D layered structure with water intercalated between sheets. The sheets are composed of {hor_ellipsis}M-[NCNCN]{sub 2}-M-bpym-M-[NCNCN]{sub 2}-M{hor_ellipsis} chains, which are linked together by dicyanamides. 21--c are isomorphic with the unit cell parameters amore » = 17.5112(4) {angstrom}, b = 11.9955(4) {angstrom}, c = 7.4684(2) {angstrom} for 2a, a = 17.5814(7) {angstrom}, b = 11.9453(5) {angstrom}, c - 7.3292(3) {angstrom} for 2b, a = 17.8642(2) {angstrom}, b = 11.9216(2) {angstrom}, c = 7.2860(2) {angstrom} for 2c, and Z = 4 for all. They crystallize as chains containing metal centers coordinated to two bridging dicyanamides, one terminal dicyanamide, one terminal chelating bpym, and one water molecule. 2a--c are the first examples of compounds containing terminal and {mu}-bound dicyanamides in the same structure. The broad maximum in the magnetic susceptibility of 1 could not be fit to any known dimer models. However, the high-temperature data were fit to the Curie-Weiss expression with g = 2.86 and {theta} = {minus}42 K. 2a--c could best be modeled as uniform 1-D chains with g = 2.04, {theta} = {minus}0.76, and J/{kappa}{sub B} = {minus}0.15 K for 2a, g = 2.34, {theta} = {minus}7.6, and J/{kappa}{sub B} = {minus}0.42 K for 2b, and g = 2.58, {theta} = {minus}5.4, and J/{kappa}{sub B} = {minus}1.42 K for 2c. Because of small exchange coupling throughout the extended networks, no long-range magnetic ordering was observed.« less
  • Trace amounts of H/sub 2/O and limited exposure to air of reaction mixtures of UCl/sub 4/ and 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, or dibenzo-18-crown-6 in 1:3 mixtures of CH/sub 3/OH and CH/sub 3/CN resulted in the hydrolysis and oxidation of UCl/sub 4/ to (UO/sub 2/Cl/sub 4/)/sup 2/minus//. In the presence of these crown ethers, it has been possible to isolate intermediate products via crystallization of crown complexes of the (UO/sub 2/Cl/sub 4/)/sup 2/minus// ion, the (UCl/sub 6/)/sup 2/minus// ion, and (UO/sub 2/Cl/sub 2/(OH/sub 2/)/sub 3/). The neutral moiety crystallizes as a hydrogen-bonded crown ether complex; however, crown ether complexation of amore » counterion, either an ammonium ion formed during the oxidation of U(IV) or a Na/sup +/ ion leached from glass reaction vessels, resulted in novel crystalline complexes of the ionic species. ((NH/sub 4/)(15-crown-5)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN, ((NH/sub 4/)(benzo-15-crown-5)/sub 2/)/sub 2/(UCl/sub 6/) /times/ 4CH/sub 3/CN, and ((NH/sub 4/)(dibenzo-18-crown-6))/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN have been structurally characterized by single-crystal X-ray diffraction techniques. The results of all the crystal studies are presented in detail. The ammonium ions interact with the crown ethers via hydrogen-bonding and electrostatic interactions. 15-Crown-5 and benzo-15-crown-5 form 2:1 sandwich cations, allowing no H/sub 4/N/sup +//hor ellipsis/(UO/sub 2/Cl/sub 4/)/sup 2/minus// interaction. The dibenzo-18-crown-6 complexed ammonium ions are 1:1 and form bifurcated hydrogen bonds with the chlorine atoms in the (UO/sub 2/Cl/sub 4/)/sup /minus// anion. The formation of (Na(12-crown-4)/sub 2//sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2OHMe and (UO/sub 2/Cl/sub 2/(OH)/sub 2/)/sub 3/) /times/ 18-crown-6 /times/ H/sub 2/O /times/ OHMe has been confirmed by preliminary single-crystal X-ray diffraction studies.« less