Probing Framework-Restricted Metal Axial Ligation and Spin State Patterns in a Post-Synthetically Reduced Iron-Porphyrin-Based Metal-Organic Framework.

An iron-porphyrin-based metal organic framework PCN-222(Fe) is investigated upon postsynthetic reduction with piperidine. Fe K-edge X-ray absorption and Kβ mainline emission spectroscopy measurements reveal the local coordination geometry, oxidation, and spin state changes experienced by the Fe sites upon reaction with this axially coordinating reducing agent. Analysis and fitting of these data confirm the binding pattern predicted by a space-filling model of the structurally constrained pore environments. These results are further supported by UV-vis diffuse reflectance, IR, and resonance Raman spectroscopy data.

[1]  B. Braun,et al.  Abrupt versus Gradual Spin-Crossover in Fe(II)(phen)2(NCS)2 and Fe(III)(dedtc)3 Compared by X-ray Absorption and Emission Spectroscopy and Quantum-Chemical Calculations. , 2015, Inorganic chemistry.

[2]  G. McIntyre,et al.  Intermolecular interactions in solid-state metalloporphyrins and their impacts on crystal and molecular structures. , 2014, Inorganic chemistry.

[3]  W. Xu,et al.  Spectroscopic study and electronic structure of prototypical iron porphyrins and their $\mu$-oxo-dimer derivatives with different functional configurations , 2014 .

[4]  Shengqian Ma,et al.  Metal-metalloporphyrin frameworks: a resurging class of functional materials. , 2014, Chemical Society reviews.

[5]  K. Hodgson,et al.  X-ray absorption spectroscopic investigation of the electronic structure differences in solution and crystalline oxyhemoglobin , 2013, Proceedings of the National Academy of Sciences.

[6]  Jyhfu Lee,et al.  Chemical bond characterization of a mixed-valence tri-cobalt complex, Co3(μ-admtrz)4(μ-OH)2(CN)6·2H2O. , 2013, Inorganic chemistry.

[7]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[8]  Cheng Wang,et al.  Metal-organic frameworks as a tunable platform for designing functional molecular materials. , 2013, Journal of the American Chemical Society.

[9]  K. Hodgson,et al.  Iron L-edge X-ray absorption spectroscopy of oxy-picket fence porphyrin: experimental insight into Fe-O2 bonding. , 2013, Journal of the American Chemical Society.

[10]  B. Hoffman,et al.  Electronic spectra of porphyrins in the solid state: Newly observed transitions, collective and structural effects, and protein-mimicking environments , 2013 .

[11]  Shengqian Ma,et al.  Biomimetic catalysis of a porous iron-based metal-metalloporphyrin framework. , 2012, Inorganic chemistry.

[12]  Zhangwen Wei,et al.  Zirconium-metalloporphyrin PCN-222: mesoporous metal-organic frameworks with ultrahigh stability as biomimetic catalysts. , 2012, Angewandte Chemie.

[13]  D. Cascio,et al.  Synthesis, structure, and metalation of two new highly porous zirconium metal-organic frameworks. , 2012, Inorganic chemistry.

[14]  Abraham M. Shultz,et al.  Active-site-accessible, porphyrinic metal-organic framework materials. , 2011, Journal of the American Chemical Society.

[15]  Mohamed Salah Belkhiria,et al.  Synthesis, spectroscopic and structural characterization of the high-spin Fe(II) cyanato-N and thiocyanato-N “picket fence” porphyrin complexes , 2010 .

[16]  F. D. de Groot,et al.  The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges. , 2010, Micron.

[17]  Richard L. Lord,et al.  Cyanide: a strong-field ligand for ferrohemes and hemoproteins? , 2008, Angewandte Chemie.

[18]  B. Noll,et al.  Four-coordinate iron(II) porphyrinates: electronic configuration change by intermolecular interaction. , 2007, Inorganic chemistry.

[19]  A. Shukla,et al.  Probing the 3d spin momentum with X-ray emission spectroscopy: the case of molecular-spin transitions. , 2006, The journal of physical chemistry. B.

[20]  A. Shukla,et al.  Temperature- and pressure-induced spin-state transitions in LaCoO 3 , 2005, cond-mat/0510569.

[21]  H. Mao,et al.  Spin transition of iron in magnesiowüstite in the Earth's lower mantle , 2005, Nature.

[22]  Scott R. Wilson,et al.  Microporous porphyrin solids. , 2005, Accounts of chemical research.

[23]  Guillaume Fiquet,et al.  Electronic Transitions in Perovskite: Possible Nonconvecting Layers in the Lower Mantle , 2004, Science.

[24]  F. D. Groot,et al.  High-Resolution X-ray Emission and X-ray Absorption Spectroscopy , 2001 .

[25]  D. Urch,et al.  Metal Kβ X-ray emission spectra of first row transition metal compounds , 2001 .

[26]  H. Mao,et al.  Magnetism in FeO at Megabar Pressures from X-Ray Emission Spectroscopy , 1999 .

[27]  K. Hodgson,et al.  A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes , 1997 .

[28]  M. Chance,et al.  Iron L-Edge X-ray Absorption Spectroscopy of Myoglobin Complexes and Photolysis Products , 1997 .

[29]  S. Cramer,et al.  Spin-polarized and site-selective X-ray absorption. Demonstration with Fe porphyrins and Kβ detection , 1995 .

[30]  W. H. Armstrong,et al.  High-resolution manganese X-ray fluorescence spectroscopy. Oxidation-state and spin-state sensitivity , 1994 .

[31]  K. Kadish,et al.  Electrochemistry of iron porphyrins under a carbon monoxide atmosphere. Interactions between carbon monoxide and pyridine , 1987 .

[32]  C. E. Castro,et al.  Ligation and reduction of iron(III) porphyrins by amines. A model for cytochrome P-450 monoamine oxidase , 1986 .

[33]  J. Landrum,et al.  Structure of bis(pyridine)(5,10,15,20-tetraphenylporphyrinato)iron(II)–pyridine solvate, [Fe(C44H28N4)(C5H5N)2].2C5H5N , 1985 .

[34]  D. Mansuy,et al.  Resonance Raman spectra of iron tetraphenylporphyrin complexes: characterization of structure and bonding sensitive bands , 1981 .

[35]  M. Momenteau,et al.  ‘Basket handle’ porphyrins: new synthetic iron(II) complexes for oxygen binding , 1980 .

[36]  Fran Adar,et al.  Fluorescence, resonance Raman, and radiationless decay in several hemoproteins , 1976 .

[37]  K. Tsutsumi,et al.  X-ray Mn K β emission spectra of manganese oxides and manganates , 1976 .

[38]  C. Reed,et al.  Synthesis, stereochemistry, and structure-related properties of alpha, beta, gamma, delta-tetraphenylporphinatoiron(II). , 1975, Journal of the American Chemical Society.

[39]  L. Radonovich,et al.  Stereochemistry of low-spin iron porphyrins. II. Bis(piperidine)-.alpha.,.beta.,.gamma.,.delta.-tetraphenylporphinatoiron(II) , 1972 .

[40]  H. Kobayashi,et al.  Electronic Spectra and Electronic Structure of Iron(II) Tetraphenylporphins , 1972 .

[41]  Mario Ulises Delgado-Jaime,et al.  Blueprint XAS: a Matlab-based toolbox for the fitting and analysis of XAS spectra. , 2010, Journal of synchrotron radiation.

[42]  Uwe Bergmann,et al.  High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information , 2005 .

[43]  G. Tourillon,et al.  X-Ray absorption spectroscopy of iron-(II) and -(III) basket-handle porphyrins , 1992 .

[44]  K. Nakamoto,et al.  Structure sensitive bands in the vibrational spectra of metal complexes of tetraphenylporphine , 1984 .