Bonding Scheme, Hydride Character, and Magnetic Paths of (HPO3)2– Versus (SeO3)2– Building Units in Solids

The abilities of the (HPO3)2– and (SeO3)2– anions as structure building units and as spin exchange paths between magnetic ions were investigated by preparing and analyzing the isostructural Fe2(SeO3)3 and Fe2(HPO3)3. In both compounds, the face-sharing Fe2O9 dimers are interconnected into chains by the (HPO3)2– and (SeO3)2– anions. The (HPO3)2– is the structural counterpart of the Se electron lone pair of (SeO3)2– due to the weak hydride character of the terminal hydrogen. However, they differ considerably as spin exchange paths between magnetic cations. Both compounds exhibit an effective magnetic dimer behavior, unexpectedly arising from the interdimer Fe—O···O—Fe exchange along the chain, but weaker in Fe2(HPO3)3 by a factor of ∼3. It is consistent with the general tendencies of the phosphite anions to act as a weak magnetic mediator, which is caused by the through-bond effect of the P3+ ion in the Fe—O···P3+···O—Fe exchange path, much weaker than in the selenite phase in absence of P3+d contribution. ...

[1]  A. Maignan,et al.  Polar Space Group and Complex Magnetism in Ni11□(HPO3)8(OH)6: Towards a New Multiferroic Material? , 2015 .

[2]  Lin Du,et al.  Positively Charged Phosphorus as a Hydrogen Bond Acceptor. , 2014, The journal of physical chemistry letters.

[3]  H. Pang,et al.  Microporous Ni₁₁(HPO₃)₈(OH)₆ nanocrystals for high-performance flexible asymmetric all solid-state supercapacitors. , 2014, Dalton transactions.

[4]  M. Johnsson,et al.  Crystal structure and magnetic properties of FeSeO(3)F--alternating antiferromagnetic S = 5/2 chains. , 2014, Inorganic chemistry.

[5]  R. David,et al.  Two-orbital three-electron stabilizing interaction for direct Co2+ - As3+ bonds involving square-planar CoO4 in BaCoAs2O5. , 2014, Angewandte Chemie.

[6]  D. Venegas‐Yazigi,et al.  Six novel transition-metal phosphite compounds, with structure related to yavapaiite: Crystal structures and magnetic and thermal properties of AI[MIII(HPO3)2] (A=K, NH4, Rb and M=V, Fe) , 2013 .

[7]  Xingao Gong,et al.  Magnetic properties and energy-mapping analysis. , 2013, Dalton transactions.

[8]  P. Fernandes,et al.  Theoretical insights into the catalytic mechanism of β-hexosaminidase , 2011 .

[9]  S. Natarajan,et al.  Synthesis, structure, and polymorphism studies in amine-templated open-framework zinc phosphites. , 2008, Inorganic chemistry.

[10]  B. Hanson,et al.  Syntheses, structures, and magnetic properties of inorganic-organic hybrid cobalt(II) phosphites containing bifunctional ligands. , 2006, Inorganic chemistry.

[11]  E. Gaudin,et al.  Synthesis, crystal structure, magnetic properties, and electronic structure of the new ternary vanadate CuMnVO4. , 2005, Inorganic chemistry.

[12]  Dadi Dai,et al.  Spin exchange interactions and magnetic structures of extended magnetic solids with localized spins: theoretical descriptions on formal, quantitative and qualitative levels , 2003 .

[13]  T. Schleid,et al.  Sc2Se3O9: Scandium(III) Oxoselenate(IV) According to Sc2[SeO3]3 with a Hexagonal "Lone-Pair" Channel Structure , 2003 .

[14]  M. Henry.  Nonempirical quantification of molecular interactions in supramolecular assemblies. , 2002, Chemphyschem : a European journal of chemical physics and physical chemistry.

[15]  C. Humphreys,et al.  Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study , 1998 .

[16]  P. Amorós,et al.  Synthetic Pathways for New Tubular Transition Metal Hydroxo- and Fluoro-Selenites: Crystal Structures ofM12(X)2(SeO3)8(OH)6(M = Co2+, Ni2+;X= OH−) , 1996 .

[17]  P. Gütlich,et al.  Ferric Phosphite: Dimers of Face-Sharing FeIIIO6 Octahedra. Crystal Structure Redetermination, Mössbauer Spectra, Magnetic Susceptibility, and Heat Capacity Data , 1994 .

[18]  G. Giester,et al.  Synthesis and crystal structure of iron(III) selenate(IV) trihydrate, Fe2(SeO3)3 • 3H2O , 1994 .

[19]  A. Cheetham,et al.  Synthesis and structures of two isostructural phosphites, Fe11(HPO3)8(OH)6 and Mn11(HPO3)8(OH)6 , 1994 .

[20]  A. Cheetham,et al.  Synthesis and structures of two isostructural phosphites, Al2(HPO3)3 and Ga2(HPO3)3 , 1994 .

[21]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[22]  G. Giester.  The Crystal Structure of Fe2(SeO3)3· H2O , 1993 .

[23]  Thomas C. Farrar,et al.  Experimental and theoretical studies of the phosphorus-hydrogen bond length and stretching mode of the phosphite anion , 1993 .

[24]  L. Cot,et al.  Structure du phosphite de fer: Fe2(PO3H)3 , 1991 .

[25]  J. Loub.  Crystal Chemistry of Inorganic Phosphites , 1991 .

[26]  Leland C. Allen,et al.  Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms , 1989 .

[27]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[28]  F. Hawthorne.  The crystal structure of mandarinoite, Fe (super 3+) 2 Se 3 O 9 .6H 2 O , 1984 .

[29]  Frank Weinhold,et al.  Natural hybrid orbitals , 1980 .

[30]  M. Tournoux,et al.  Localisation du doublet solitaire dans les composés oxygènés cristallisés du thallium I , 1978 .

[31]  A. Allred,et al.  Electronegativity values from thermochemical data , 1961 .

[32]  P. Jönsson,et al.  The magnetic structure and properties of rhombohedral Li3Fe2(PO4)3. , 2000 .

[33]  J. Attfield,et al.  Novel crystalline microporous transition-metal phosphites M11(HPO3)8(OH)6 (M = Zn, Co, Ni). X-ray powder diffraction structure determination of the cobalt and nickel derivatives , 1993 .

[34]  G. Long.  A Mössbauer Effect And Magnetic Study of Fe2(SO4)3 and Fe2(MoO4)3, Two L-Type Ferrimagnets , 1984 .