Rational synthesis of unidimensional mixed valence solids. Structural, spectral, and electrical studies of charge distribution and transport in partially oxidized nickel and palladium bisdiphenylglyoximates
A detailed study is presented of solid-state structure, oxidation state, and electron transport in Ni(dpg)/sub 2/I and Pg(dpg)/sub 2/I, dpg = diphenylglyoximato. The crystal structure of Ni(dpg)/sub 2/I has been studied by x-ray diffraction at 23 and -160/sup 0/C. The compound crystallizes in the te...
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| Veröffentlicht in: | J. Am. Chem. Soc.; (United States) 1979-05, Vol.101 (11), p.2921-2936 |
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| container_title | J. Am. Chem. Soc.; (United States) |
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| creator | Cowie, Martin Gleizes, Alain Grynkewich, Gregory W Kalina, Davida Webster McClure, Malcolm S Scaringe, Raymond P Teitelbaum, Robert C Ruby, Stanley L Ibers, James A |
| description | A detailed study is presented of solid-state structure, oxidation state, and electron transport in Ni(dpg)/sub 2/I and Pg(dpg)/sub 2/I, dpg = diphenylglyoximato. The crystal structure of Ni(dpg)/sub 2/I has been studied by x-ray diffraction at 23 and -160/sup 0/C. The compound crystallizes in the tetragonal space group D/sub 4h//sup 8/-P4/ncc, with four formula units of Ni(dpg)/sub 2/I in a unit cell having dimensions at -160/sup 0/C of a = 19.774 (8), c = 6.446 (3) A. Full-matrix least-squares refinement of 31 variables gave a final value of the conventional R index (on F) of 0.093 for 353 reflections having F/sub 0//sup 2/ > 3 sigma(F/sub 0//sup 2/). The crystal structure consists of stacked Ni(dpg)/sub 2/ units (staggered by 90/sup 0/) and disordered chains of iodine atoms extending in the c direction. At -160/sup 0/C the Ni--Ni separation is 3.223 (2) A; other important distances are Ni--N = 1.868 (15), N--C = 1.33 (3), N--O = 1.34 (3) A. The Ni(dpg)/sub 2/ moiety is decidedly nonplanar (D/sub 2/ symmetry) with coordinated N atoms displaced 0.12 (2) A above or below the mean molecular plane. Analysis of diffuse x-ray scattering associated with the disordered iodine chains is consistent with I/sub 5//sup -/ being the predominant species. This result is in agreement with resonance Raman spectroscopic studies on Ni(dpg)/sub 2/I and Pd(dpg)/sub 2/I as well as on model compounds. Fundamental polyiodide transitions in the M(dpg)/sub 2/I materials are observed(..nu../sub 0/ = 4880--6471 A)at 161 vs and 107 w cm/sup -1/; weak M(dpg)/sub 2/-centered scattering is also noted. Iodination brings about an increase in conductivity of > 10/sup 8/ (Ni) and > 10/sup 7/ (Pd), which is especially noteworthy since the only major change in crystal structure upon iodination is a ca. 0.27 A decrease in the M(dpg)/sub 2/ stacking distance. Variable-temperature studies show the Ni(dpg)/sub 2/I and Pd(dpg)/sub 2/I conductivities to be thermally activated. |
| doi_str_mv | 10.1021/ja00505a021 |
| format | Article |
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Structural, spectral, and electrical studies of charge distribution and transport in partially oxidized nickel and palladium bisdiphenylglyoximates</title><source>ACS Publications</source><creator>Cowie, Martin ; Gleizes, Alain ; Grynkewich, Gregory W ; Kalina, Davida Webster ; McClure, Malcolm S ; Scaringe, Raymond P ; Teitelbaum, Robert C ; Ruby, Stanley L ; Ibers, James A</creator><creatorcontrib>Cowie, Martin ; Gleizes, Alain ; Grynkewich, Gregory W ; Kalina, Davida Webster ; McClure, Malcolm S ; Scaringe, Raymond P ; Teitelbaum, Robert C ; Ruby, Stanley L ; Ibers, James A ; Northwestern Univ., Evanston, IL</creatorcontrib><description>A detailed study is presented of solid-state structure, oxidation state, and electron transport in Ni(dpg)/sub 2/I and Pg(dpg)/sub 2/I, dpg = diphenylglyoximato. The crystal structure of Ni(dpg)/sub 2/I has been studied by x-ray diffraction at 23 and -160/sup 0/C. The compound crystallizes in the tetragonal space group D/sub 4h//sup 8/-P4/ncc, with four formula units of Ni(dpg)/sub 2/I in a unit cell having dimensions at -160/sup 0/C of a = 19.774 (8), c = 6.446 (3) A. Full-matrix least-squares refinement of 31 variables gave a final value of the conventional R index (on F) of 0.093 for 353 reflections having F/sub 0//sup 2/ > 3 sigma(F/sub 0//sup 2/). The crystal structure consists of stacked Ni(dpg)/sub 2/ units (staggered by 90/sup 0/) and disordered chains of iodine atoms extending in the c direction. At -160/sup 0/C the Ni--Ni separation is 3.223 (2) A; other important distances are Ni--N = 1.868 (15), N--C = 1.33 (3), N--O = 1.34 (3) A. The Ni(dpg)/sub 2/ moiety is decidedly nonplanar (D/sub 2/ symmetry) with coordinated N atoms displaced 0.12 (2) A above or below the mean molecular plane. Analysis of diffuse x-ray scattering associated with the disordered iodine chains is consistent with I/sub 5//sup -/ being the predominant species. This result is in agreement with resonance Raman spectroscopic studies on Ni(dpg)/sub 2/I and Pd(dpg)/sub 2/I as well as on model compounds. Fundamental polyiodide transitions in the M(dpg)/sub 2/I materials are observed(..nu../sub 0/ = 4880--6471 A)at 161 vs and 107 w cm/sup -1/; weak M(dpg)/sub 2/-centered scattering is also noted. Iodination brings about an increase in conductivity of > 10/sup 8/ (Ni) and > 10/sup 7/ (Pd), which is especially noteworthy since the only major change in crystal structure upon iodination is a ca. 0.27 A decrease in the M(dpg)/sub 2/ stacking distance. Variable-temperature studies show the Ni(dpg)/sub 2/I and Pd(dpg)/sub 2/I conductivities to be thermally activated.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00505a021</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>400201 - Chemical & Physicochemical Properties ; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) ; ACTIVATION ENERGY ; AROMATICS ; BOND ANGLE ; CHARGE DISTRIBUTION ; CHEMICAL PREPARATION ; CHLORINATED AROMATIC HYDROCARBONS ; COHERENT SCATTERING ; COMPARATIVE EVALUATIONS ; COMPLEXES ; CRYSTAL LATTICES ; CRYSTAL STRUCTURE ; CRYSTALS ; DATA ; DATA FORMS ; DIFFRACTION ; DISTANCE ; ELECTRIC CONDUCTIVITY ; ELECTRICAL PROPERTIES ; ELECTRON SPECTROSCOPY ; ENERGY ; ESTERS ; EXPERIMENTAL DATA ; GAMMA SPECTROMETERS ; HALIDES ; HALOGEN COMPOUNDS ; HALOGENATED AROMATIC HYDROCARBONS ; HETEROCYCLIC COMPOUNDS ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; INTERATOMIC DISTANCES ; IODIDES ; IODINE COMPOUNDS ; ISOLATED VALUES ; ISOMER SHIFT ; LEAST SQUARE FIT ; LOW TEMPERATURE ; MAXIMUM-LIKELIHOOD FIT ; MEASURING INSTRUMENTS ; MEDIUM TEMPERATURE ; MOESSBAUER SPECTROMETERS ; MOLECULAR STRUCTURE ; MONOCRYSTALS ; NICKEL COMPLEXES ; NICKEL COMPOUNDS ; NICKEL IODIDES ; NUMERICAL DATA ; NUMERICAL SOLUTION ; ORGANIC CHLORINE COMPOUNDS ; ORGANIC COMPOUNDS ; ORGANIC HALOGEN COMPOUNDS ; ORGANIC NITROGEN COMPOUNDS ; ORGANIC OXYGEN COMPOUNDS ; ORGANIC SOLVENTS ; ORGANOMETALLIC COMPOUNDS ; PALLADIUM COMPLEXES ; PHOTOELECTRON SPECTROSCOPY ; PHYSICAL PROPERTIES ; RAMAN SPECTRA ; SCATTERING ; SOLVENTS ; SPECTRA ; SPECTROMETERS ; SPECTROSCOPY ; STOICHIOMETRY ; STRUCTURAL CHEMICAL ANALYSIS ; SYNTHESIS ; TEMPERATURE DEPENDENCE ; TETRAGONAL LATTICES ; TRANSITION ELEMENT COMPLEXES ; TRANSITION ELEMENT COMPOUNDS ; VALENCE ; X-RAY DIFFRACTION</subject><ispartof>J. Am. Chem. Soc.; (United States), 1979-05, Vol.101 (11), p.2921-2936</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a309t-aa188359f619256a8b8408190cd22214c1f68497a6c535d9d87892af5467f9793</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja00505a021$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja00505a021$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,881,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/6063542$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Cowie, Martin</creatorcontrib><creatorcontrib>Gleizes, Alain</creatorcontrib><creatorcontrib>Grynkewich, Gregory W</creatorcontrib><creatorcontrib>Kalina, Davida Webster</creatorcontrib><creatorcontrib>McClure, Malcolm S</creatorcontrib><creatorcontrib>Scaringe, Raymond P</creatorcontrib><creatorcontrib>Teitelbaum, Robert C</creatorcontrib><creatorcontrib>Ruby, Stanley L</creatorcontrib><creatorcontrib>Ibers, James A</creatorcontrib><creatorcontrib>Northwestern Univ., Evanston, IL</creatorcontrib><title>Rational synthesis of unidimensional mixed valence solids. Structural, spectral, and electrical studies of charge distribution and transport in partially oxidized nickel and palladium bisdiphenylglyoximates</title><title>J. Am. Chem. Soc.; (United States)</title><addtitle>J. Am. Chem. Soc</addtitle><description>A detailed study is presented of solid-state structure, oxidation state, and electron transport in Ni(dpg)/sub 2/I and Pg(dpg)/sub 2/I, dpg = diphenylglyoximato. The crystal structure of Ni(dpg)/sub 2/I has been studied by x-ray diffraction at 23 and -160/sup 0/C. The compound crystallizes in the tetragonal space group D/sub 4h//sup 8/-P4/ncc, with four formula units of Ni(dpg)/sub 2/I in a unit cell having dimensions at -160/sup 0/C of a = 19.774 (8), c = 6.446 (3) A. Full-matrix least-squares refinement of 31 variables gave a final value of the conventional R index (on F) of 0.093 for 353 reflections having F/sub 0//sup 2/ > 3 sigma(F/sub 0//sup 2/). The crystal structure consists of stacked Ni(dpg)/sub 2/ units (staggered by 90/sup 0/) and disordered chains of iodine atoms extending in the c direction. At -160/sup 0/C the Ni--Ni separation is 3.223 (2) A; other important distances are Ni--N = 1.868 (15), N--C = 1.33 (3), N--O = 1.34 (3) A. The Ni(dpg)/sub 2/ moiety is decidedly nonplanar (D/sub 2/ symmetry) with coordinated N atoms displaced 0.12 (2) A above or below the mean molecular plane. Analysis of diffuse x-ray scattering associated with the disordered iodine chains is consistent with I/sub 5//sup -/ being the predominant species. This result is in agreement with resonance Raman spectroscopic studies on Ni(dpg)/sub 2/I and Pd(dpg)/sub 2/I as well as on model compounds. Fundamental polyiodide transitions in the M(dpg)/sub 2/I materials are observed(..nu../sub 0/ = 4880--6471 A)at 161 vs and 107 w cm/sup -1/; weak M(dpg)/sub 2/-centered scattering is also noted. Iodination brings about an increase in conductivity of > 10/sup 8/ (Ni) and > 10/sup 7/ (Pd), which is especially noteworthy since the only major change in crystal structure upon iodination is a ca. 0.27 A decrease in the M(dpg)/sub 2/ stacking distance. Variable-temperature studies show the Ni(dpg)/sub 2/I and Pd(dpg)/sub 2/I conductivities to be thermally activated.</description><subject>400201 - Chemical & Physicochemical Properties</subject><subject>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</subject><subject>ACTIVATION ENERGY</subject><subject>AROMATICS</subject><subject>BOND ANGLE</subject><subject>CHARGE DISTRIBUTION</subject><subject>CHEMICAL PREPARATION</subject><subject>CHLORINATED AROMATIC HYDROCARBONS</subject><subject>COHERENT SCATTERING</subject><subject>COMPARATIVE EVALUATIONS</subject><subject>COMPLEXES</subject><subject>CRYSTAL LATTICES</subject><subject>CRYSTAL STRUCTURE</subject><subject>CRYSTALS</subject><subject>DATA</subject><subject>DATA FORMS</subject><subject>DIFFRACTION</subject><subject>DISTANCE</subject><subject>ELECTRIC CONDUCTIVITY</subject><subject>ELECTRICAL PROPERTIES</subject><subject>ELECTRON SPECTROSCOPY</subject><subject>ENERGY</subject><subject>ESTERS</subject><subject>EXPERIMENTAL DATA</subject><subject>GAMMA SPECTROMETERS</subject><subject>HALIDES</subject><subject>HALOGEN COMPOUNDS</subject><subject>HALOGENATED AROMATIC HYDROCARBONS</subject><subject>HETEROCYCLIC COMPOUNDS</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>INTERATOMIC DISTANCES</subject><subject>IODIDES</subject><subject>IODINE COMPOUNDS</subject><subject>ISOLATED VALUES</subject><subject>ISOMER SHIFT</subject><subject>LEAST SQUARE FIT</subject><subject>LOW TEMPERATURE</subject><subject>MAXIMUM-LIKELIHOOD FIT</subject><subject>MEASURING INSTRUMENTS</subject><subject>MEDIUM TEMPERATURE</subject><subject>MOESSBAUER SPECTROMETERS</subject><subject>MOLECULAR STRUCTURE</subject><subject>MONOCRYSTALS</subject><subject>NICKEL COMPLEXES</subject><subject>NICKEL COMPOUNDS</subject><subject>NICKEL IODIDES</subject><subject>NUMERICAL DATA</subject><subject>NUMERICAL SOLUTION</subject><subject>ORGANIC CHLORINE COMPOUNDS</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC HALOGEN COMPOUNDS</subject><subject>ORGANIC NITROGEN COMPOUNDS</subject><subject>ORGANIC OXYGEN COMPOUNDS</subject><subject>ORGANIC SOLVENTS</subject><subject>ORGANOMETALLIC COMPOUNDS</subject><subject>PALLADIUM COMPLEXES</subject><subject>PHOTOELECTRON SPECTROSCOPY</subject><subject>PHYSICAL PROPERTIES</subject><subject>RAMAN SPECTRA</subject><subject>SCATTERING</subject><subject>SOLVENTS</subject><subject>SPECTRA</subject><subject>SPECTROMETERS</subject><subject>SPECTROSCOPY</subject><subject>STOICHIOMETRY</subject><subject>STRUCTURAL CHEMICAL ANALYSIS</subject><subject>SYNTHESIS</subject><subject>TEMPERATURE DEPENDENCE</subject><subject>TETRAGONAL LATTICES</subject><subject>TRANSITION ELEMENT COMPLEXES</subject><subject>TRANSITION ELEMENT COMPOUNDS</subject><subject>VALENCE</subject><subject>X-RAY DIFFRACTION</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1979</creationdate><recordtype>article</recordtype><recordid>eNptkc9u1DAQxiMEEkvhxAtYXDhAiu3ETnJEK_5JK6jacrZmbafrrdeJPA7a8JB9pno3CHHg5Bl9P38z9lcUrxm9ZJSzD3ugVFABuX5SrJjgtBSMy6fFilLKy6aV1fPiBeI-tzVv2ap4uIbkhgCe4BzSzqJDMvRkCs64gw24aAd3tIb8Am-DtgQH7wxekpsUJ52mCP49wdHqdK4gGGL9qXP6ZJsm4-zZVO8g3lliHGZtO53mnul8L-A4xERcICPE5MD7mQzHvMPvPDc4fW_9GR2zAsZNB7J1aNy4s2H2d37O7AGSxZfFsx482ld_zovi5-dPt-uv5ebHl2_rj5sSKtqlEoC1bSW6XrKOCwnttq1pyzqqDeec1Zr1sq27BqQWlTCdaZu249CLWjZ913TVRfFm8R0wOYXaJat3egghv1tJKitR8wy9WyAdB8RoezXGvGacFaPqlJf6J69Mlwudv8ce_6IQ75Vsqkao26sbVa3rTXPNv6urzL9deNCo9sMUc1D4X-dHcvmpLQ</recordid><startdate>197905</startdate><enddate>197905</enddate><creator>Cowie, Martin</creator><creator>Gleizes, Alain</creator><creator>Grynkewich, Gregory W</creator><creator>Kalina, Davida Webster</creator><creator>McClure, Malcolm S</creator><creator>Scaringe, Raymond P</creator><creator>Teitelbaum, Robert C</creator><creator>Ruby, Stanley L</creator><creator>Ibers, James A</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>197905</creationdate><title>Rational synthesis of unidimensional mixed valence solids. Structural, spectral, and electrical studies of charge distribution and transport in partially oxidized nickel and palladium bisdiphenylglyoximates</title><author>Cowie, Martin ; Gleizes, Alain ; Grynkewich, Gregory W ; Kalina, Davida Webster ; McClure, Malcolm S ; Scaringe, Raymond P ; Teitelbaum, Robert C ; Ruby, Stanley L ; Ibers, James A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a309t-aa188359f619256a8b8408190cd22214c1f68497a6c535d9d87892af5467f9793</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1979</creationdate><topic>400201 - Chemical & Physicochemical Properties</topic><topic>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</topic><topic>ACTIVATION ENERGY</topic><topic>AROMATICS</topic><topic>BOND ANGLE</topic><topic>CHARGE DISTRIBUTION</topic><topic>CHEMICAL PREPARATION</topic><topic>CHLORINATED AROMATIC HYDROCARBONS</topic><topic>COHERENT SCATTERING</topic><topic>COMPARATIVE EVALUATIONS</topic><topic>COMPLEXES</topic><topic>CRYSTAL LATTICES</topic><topic>CRYSTAL STRUCTURE</topic><topic>CRYSTALS</topic><topic>DATA</topic><topic>DATA FORMS</topic><topic>DIFFRACTION</topic><topic>DISTANCE</topic><topic>ELECTRIC CONDUCTIVITY</topic><topic>ELECTRICAL PROPERTIES</topic><topic>ELECTRON SPECTROSCOPY</topic><topic>ENERGY</topic><topic>ESTERS</topic><topic>EXPERIMENTAL DATA</topic><topic>GAMMA SPECTROMETERS</topic><topic>HALIDES</topic><topic>HALOGEN COMPOUNDS</topic><topic>HALOGENATED AROMATIC HYDROCARBONS</topic><topic>HETEROCYCLIC COMPOUNDS</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>INTERATOMIC DISTANCES</topic><topic>IODIDES</topic><topic>IODINE COMPOUNDS</topic><topic>ISOLATED VALUES</topic><topic>ISOMER SHIFT</topic><topic>LEAST SQUARE FIT</topic><topic>LOW TEMPERATURE</topic><topic>MAXIMUM-LIKELIHOOD FIT</topic><topic>MEASURING INSTRUMENTS</topic><topic>MEDIUM TEMPERATURE</topic><topic>MOESSBAUER SPECTROMETERS</topic><topic>MOLECULAR STRUCTURE</topic><topic>MONOCRYSTALS</topic><topic>NICKEL COMPLEXES</topic><topic>NICKEL COMPOUNDS</topic><topic>NICKEL IODIDES</topic><topic>NUMERICAL DATA</topic><topic>NUMERICAL SOLUTION</topic><topic>ORGANIC CHLORINE COMPOUNDS</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC HALOGEN COMPOUNDS</topic><topic>ORGANIC NITROGEN COMPOUNDS</topic><topic>ORGANIC OXYGEN COMPOUNDS</topic><topic>ORGANIC SOLVENTS</topic><topic>ORGANOMETALLIC COMPOUNDS</topic><topic>PALLADIUM COMPLEXES</topic><topic>PHOTOELECTRON SPECTROSCOPY</topic><topic>PHYSICAL PROPERTIES</topic><topic>RAMAN SPECTRA</topic><topic>SCATTERING</topic><topic>SOLVENTS</topic><topic>SPECTRA</topic><topic>SPECTROMETERS</topic><topic>SPECTROSCOPY</topic><topic>STOICHIOMETRY</topic><topic>STRUCTURAL CHEMICAL ANALYSIS</topic><topic>SYNTHESIS</topic><topic>TEMPERATURE DEPENDENCE</topic><topic>TETRAGONAL LATTICES</topic><topic>TRANSITION ELEMENT COMPLEXES</topic><topic>TRANSITION ELEMENT COMPOUNDS</topic><topic>VALENCE</topic><topic>X-RAY DIFFRACTION</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cowie, Martin</creatorcontrib><creatorcontrib>Gleizes, Alain</creatorcontrib><creatorcontrib>Grynkewich, Gregory W</creatorcontrib><creatorcontrib>Kalina, Davida Webster</creatorcontrib><creatorcontrib>McClure, Malcolm S</creatorcontrib><creatorcontrib>Scaringe, Raymond P</creatorcontrib><creatorcontrib>Teitelbaum, Robert C</creatorcontrib><creatorcontrib>Ruby, Stanley L</creatorcontrib><creatorcontrib>Ibers, James A</creatorcontrib><creatorcontrib>Northwestern Univ., Evanston, IL</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Am. Chem. Soc.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cowie, Martin</au><au>Gleizes, Alain</au><au>Grynkewich, Gregory W</au><au>Kalina, Davida Webster</au><au>McClure, Malcolm S</au><au>Scaringe, Raymond P</au><au>Teitelbaum, Robert C</au><au>Ruby, Stanley L</au><au>Ibers, James A</au><aucorp>Northwestern Univ., Evanston, IL</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Rational synthesis of unidimensional mixed valence solids. Structural, spectral, and electrical studies of charge distribution and transport in partially oxidized nickel and palladium bisdiphenylglyoximates</atitle><jtitle>J. Am. Chem. Soc.; (United States)</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1979-05</date><risdate>1979</risdate><volume>101</volume><issue>11</issue><spage>2921</spage><epage>2936</epage><pages>2921-2936</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>A detailed study is presented of solid-state structure, oxidation state, and electron transport in Ni(dpg)/sub 2/I and Pg(dpg)/sub 2/I, dpg = diphenylglyoximato. The crystal structure of Ni(dpg)/sub 2/I has been studied by x-ray diffraction at 23 and -160/sup 0/C. The compound crystallizes in the tetragonal space group D/sub 4h//sup 8/-P4/ncc, with four formula units of Ni(dpg)/sub 2/I in a unit cell having dimensions at -160/sup 0/C of a = 19.774 (8), c = 6.446 (3) A. Full-matrix least-squares refinement of 31 variables gave a final value of the conventional R index (on F) of 0.093 for 353 reflections having F/sub 0//sup 2/ > 3 sigma(F/sub 0//sup 2/). The crystal structure consists of stacked Ni(dpg)/sub 2/ units (staggered by 90/sup 0/) and disordered chains of iodine atoms extending in the c direction. At -160/sup 0/C the Ni--Ni separation is 3.223 (2) A; other important distances are Ni--N = 1.868 (15), N--C = 1.33 (3), N--O = 1.34 (3) A. The Ni(dpg)/sub 2/ moiety is decidedly nonplanar (D/sub 2/ symmetry) with coordinated N atoms displaced 0.12 (2) A above or below the mean molecular plane. Analysis of diffuse x-ray scattering associated with the disordered iodine chains is consistent with I/sub 5//sup -/ being the predominant species. This result is in agreement with resonance Raman spectroscopic studies on Ni(dpg)/sub 2/I and Pd(dpg)/sub 2/I as well as on model compounds. Fundamental polyiodide transitions in the M(dpg)/sub 2/I materials are observed(..nu../sub 0/ = 4880--6471 A)at 161 vs and 107 w cm/sup -1/; weak M(dpg)/sub 2/-centered scattering is also noted. Iodination brings about an increase in conductivity of > 10/sup 8/ (Ni) and > 10/sup 7/ (Pd), which is especially noteworthy since the only major change in crystal structure upon iodination is a ca. 0.27 A decrease in the M(dpg)/sub 2/ stacking distance. Variable-temperature studies show the Ni(dpg)/sub 2/I and Pd(dpg)/sub 2/I conductivities to be thermally activated.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/ja00505a021</doi><tpages>16</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0002-7863 |
| ispartof | J. Am. Chem. Soc.; (United States), 1979-05, Vol.101 (11), p.2921-2936 |
| issn | 0002-7863 1520-5126 |
| language | eng |
| recordid | cdi_crossref_primary_10_1021_ja00505a021 |
| source | ACS Publications |
| subjects | 400201 - Chemical & Physicochemical Properties 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) ACTIVATION ENERGY AROMATICS BOND ANGLE CHARGE DISTRIBUTION CHEMICAL PREPARATION CHLORINATED AROMATIC HYDROCARBONS COHERENT SCATTERING COMPARATIVE EVALUATIONS COMPLEXES CRYSTAL LATTICES CRYSTAL STRUCTURE CRYSTALS DATA DATA FORMS DIFFRACTION DISTANCE ELECTRIC CONDUCTIVITY ELECTRICAL PROPERTIES ELECTRON SPECTROSCOPY ENERGY ESTERS EXPERIMENTAL DATA GAMMA SPECTROMETERS HALIDES HALOGEN COMPOUNDS HALOGENATED AROMATIC HYDROCARBONS HETEROCYCLIC COMPOUNDS INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY INTERATOMIC DISTANCES IODIDES IODINE COMPOUNDS ISOLATED VALUES ISOMER SHIFT LEAST SQUARE FIT LOW TEMPERATURE MAXIMUM-LIKELIHOOD FIT MEASURING INSTRUMENTS MEDIUM TEMPERATURE MOESSBAUER SPECTROMETERS MOLECULAR STRUCTURE MONOCRYSTALS NICKEL COMPLEXES NICKEL COMPOUNDS NICKEL IODIDES NUMERICAL DATA NUMERICAL SOLUTION ORGANIC CHLORINE COMPOUNDS ORGANIC COMPOUNDS ORGANIC HALOGEN COMPOUNDS ORGANIC NITROGEN COMPOUNDS ORGANIC OXYGEN COMPOUNDS ORGANIC SOLVENTS ORGANOMETALLIC COMPOUNDS PALLADIUM COMPLEXES PHOTOELECTRON SPECTROSCOPY PHYSICAL PROPERTIES RAMAN SPECTRA SCATTERING SOLVENTS SPECTRA SPECTROMETERS SPECTROSCOPY STOICHIOMETRY STRUCTURAL CHEMICAL ANALYSIS SYNTHESIS TEMPERATURE DEPENDENCE TETRAGONAL LATTICES TRANSITION ELEMENT COMPLEXES TRANSITION ELEMENT COMPOUNDS VALENCE X-RAY DIFFRACTION |
| title | Rational synthesis of unidimensional mixed valence solids. Structural, spectral, and electrical studies of charge distribution and transport in partially oxidized nickel and palladium bisdiphenylglyoximates |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-02T02%3A19%3A57IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-istex_osti_&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Rational%20synthesis%20of%20unidimensional%20mixed%20valence%20solids.%20Structural,%20spectral,%20and%20electrical%20studies%20of%20charge%20distribution%20and%20transport%20in%20partially%20oxidized%20nickel%20and%20palladium%20bisdiphenylglyoximates&rft.jtitle=J.%20Am.%20Chem.%20Soc.;%20(United%20States)&rft.au=Cowie,%20Martin&rft.aucorp=Northwestern%20Univ.,%20Evanston,%20IL&rft.date=1979-05&rft.volume=101&rft.issue=11&rft.spage=2921&rft.epage=2936&rft.pages=2921-2936&rft.issn=0002-7863&rft.eissn=1520-5126&rft_id=info:doi/10.1021/ja00505a021&rft_dat=%3Cistex_osti_%3Eark_67375_TPS_3C4L7R2N_P%3C/istex_osti_%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true |