The Metallic State in Neutral Radical Conductors: Dimensionality, Pressure and Multiple Orbital Effects

Pressure-induced changes in the solid-state structures and transport properties of three oxobenzene-bridged bisdithiazolyl radicals 2 (R = H, F, Ph) over the range 0–15 GPa are described. All three materials experience compression of their π-stacked architecture, be it (i) 1D ABABAB π-stack (R = Ph)...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2015-11, Vol.137 (44), p.14136-14148
Main Authors: Tian, Di, Winter, Stephen M, Mailman, Aaron, Wong, Joanne W. L, Yong, Wenjun, Yamaguchi, Hiroshi, Jia, Yating, Tse, John S, Desgreniers, Serge, Secco, Richard A, Julian, Stephen R, Jin, Changqing, Mito, Masaki, Ohishi, Yasuo, Oakley, Richard T
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-a472t-d60b09e68f43463af6b59c6af5f4db8cd8aa1959b0533c4d2ee5f193f23c75313
cites cdi_FETCH-LOGICAL-a472t-d60b09e68f43463af6b59c6af5f4db8cd8aa1959b0533c4d2ee5f193f23c75313
container_end_page 14148
container_issue 44
container_start_page 14136
container_title Journal of the American Chemical Society
container_volume 137
creator Tian, Di
Winter, Stephen M
Mailman, Aaron
Wong, Joanne W. L
Yong, Wenjun
Yamaguchi, Hiroshi
Jia, Yating
Tse, John S
Desgreniers, Serge
Secco, Richard A
Julian, Stephen R
Jin, Changqing
Mito, Masaki
Ohishi, Yasuo
Oakley, Richard T
description Pressure-induced changes in the solid-state structures and transport properties of three oxobenzene-bridged bisdithiazolyl radicals 2 (R = H, F, Ph) over the range 0–15 GPa are described. All three materials experience compression of their π-stacked architecture, be it (i) 1D ABABAB π-stack (R = Ph), (ii) quasi-1D slipped π-stack (R = H), or (iii) 2D brick-wall π-stack (R = F). While R = H undergoes two structural phase transitions, neither of R = F, Ph display any phase change. All three radicals order as spin-canted antiferromagnets, but spin-canted ordering is lost at pressures
doi_str_mv 10.1021/jacs.5b08254
format article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1732595968</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1732595968</sourcerecordid><originalsourceid>FETCH-LOGICAL-a472t-d60b09e68f43463af6b59c6af5f4db8cd8aa1959b0533c4d2ee5f193f23c75313</originalsourceid><addsrcrecordid>eNptkD1PwzAQQC0EoqWwMSOPDE3xR-wmbKiUD4lSBGWOHOcMrtyk2M7Qf0-qFliYTie9eyc9hM4pGVHC6NVS6TASJcmYSA9QnwpGEkGZPER9QghLxpnkPXQSwrJbU5bRY9RjUlBOmeijj8Un4BlE5ZzV-C2qCNjW-Bna6JXDr6qyupuTpq5aHRsfrvGtXUEdbFMrZ-NmiF88hNB6wKqu8Kx10a4d4LkvbWfFU2NAx3CKjoxyAc72c4De76aLyUPyNL9_nNw8JSods5hUkpQkB5mZlKeSKyNLkWupjDBpVWa6ypSiuchLIjjXacUAhKE5N4zrseCUD9Dlzrv2zVcLIRYrGzQ4p2po2lDQMWeiE8isQ4c7VPsmBA-mWHu7Un5TUFJs0xbbtMU-bYdf7M1tuYLqF_5p-fd6e7VsWt8FCv-7vgHwvYJj</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1732595968</pqid></control><display><type>article</type><title>The Metallic State in Neutral Radical Conductors: Dimensionality, Pressure and Multiple Orbital Effects</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read &amp; Publish Agreement 2022-2024 (Reading list)</source><creator>Tian, Di ; Winter, Stephen M ; Mailman, Aaron ; Wong, Joanne W. L ; Yong, Wenjun ; Yamaguchi, Hiroshi ; Jia, Yating ; Tse, John S ; Desgreniers, Serge ; Secco, Richard A ; Julian, Stephen R ; Jin, Changqing ; Mito, Masaki ; Ohishi, Yasuo ; Oakley, Richard T</creator><creatorcontrib>Tian, Di ; Winter, Stephen M ; Mailman, Aaron ; Wong, Joanne W. L ; Yong, Wenjun ; Yamaguchi, Hiroshi ; Jia, Yating ; Tse, John S ; Desgreniers, Serge ; Secco, Richard A ; Julian, Stephen R ; Jin, Changqing ; Mito, Masaki ; Ohishi, Yasuo ; Oakley, Richard T</creatorcontrib><description>Pressure-induced changes in the solid-state structures and transport properties of three oxobenzene-bridged bisdithiazolyl radicals 2 (R = H, F, Ph) over the range 0–15 GPa are described. All three materials experience compression of their π-stacked architecture, be it (i) 1D ABABAB π-stack (R = Ph), (ii) quasi-1D slipped π-stack (R = H), or (iii) 2D brick-wall π-stack (R = F). While R = H undergoes two structural phase transitions, neither of R = F, Ph display any phase change. All three radicals order as spin-canted antiferromagnets, but spin-canted ordering is lost at pressures &lt;1.5 GPa. At room temperature, their electrical conductivity increases rapidly with pressure, and the thermal activation energy for conduction E act is eliminated at pressures ranging from ∼3 GPa for R = F to ∼12 GPa for R = Ph, heralding formation of a highly correlated (or bad) metallic state. For R = F, H the pressure-induced Mott insulator to metal conversion has been tracked by measurements of optical conductivity at ambient temperature and electrical resistivity at low temperature. For R = F compression to 6.2 GPa leads to a quasiquadratic temperature dependence of the resistivity over the range 5–300 K, consistent with formation of a 2D Fermi liquid state. DFT band structure calculations suggest that the ease of metallization of these radicals can be ascribed to their multiorbital character. Mixing and overlap of SOMO- and LUMO-based bands affords an increased kinetic energy stabilization of the metallic state relative to a single SOMO-based band system.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.5b08254</identifier><identifier>PMID: 26513125</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 2015-11, Vol.137 (44), p.14136-14148</ispartof><rights>Copyright © 2015 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a472t-d60b09e68f43463af6b59c6af5f4db8cd8aa1959b0533c4d2ee5f193f23c75313</citedby><cites>FETCH-LOGICAL-a472t-d60b09e68f43463af6b59c6af5f4db8cd8aa1959b0533c4d2ee5f193f23c75313</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,777,781,27905,27906</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26513125$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Tian, Di</creatorcontrib><creatorcontrib>Winter, Stephen M</creatorcontrib><creatorcontrib>Mailman, Aaron</creatorcontrib><creatorcontrib>Wong, Joanne W. L</creatorcontrib><creatorcontrib>Yong, Wenjun</creatorcontrib><creatorcontrib>Yamaguchi, Hiroshi</creatorcontrib><creatorcontrib>Jia, Yating</creatorcontrib><creatorcontrib>Tse, John S</creatorcontrib><creatorcontrib>Desgreniers, Serge</creatorcontrib><creatorcontrib>Secco, Richard A</creatorcontrib><creatorcontrib>Julian, Stephen R</creatorcontrib><creatorcontrib>Jin, Changqing</creatorcontrib><creatorcontrib>Mito, Masaki</creatorcontrib><creatorcontrib>Ohishi, Yasuo</creatorcontrib><creatorcontrib>Oakley, Richard T</creatorcontrib><title>The Metallic State in Neutral Radical Conductors: Dimensionality, Pressure and Multiple Orbital Effects</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Pressure-induced changes in the solid-state structures and transport properties of three oxobenzene-bridged bisdithiazolyl radicals 2 (R = H, F, Ph) over the range 0–15 GPa are described. All three materials experience compression of their π-stacked architecture, be it (i) 1D ABABAB π-stack (R = Ph), (ii) quasi-1D slipped π-stack (R = H), or (iii) 2D brick-wall π-stack (R = F). While R = H undergoes two structural phase transitions, neither of R = F, Ph display any phase change. All three radicals order as spin-canted antiferromagnets, but spin-canted ordering is lost at pressures &lt;1.5 GPa. At room temperature, their electrical conductivity increases rapidly with pressure, and the thermal activation energy for conduction E act is eliminated at pressures ranging from ∼3 GPa for R = F to ∼12 GPa for R = Ph, heralding formation of a highly correlated (or bad) metallic state. For R = F, H the pressure-induced Mott insulator to metal conversion has been tracked by measurements of optical conductivity at ambient temperature and electrical resistivity at low temperature. For R = F compression to 6.2 GPa leads to a quasiquadratic temperature dependence of the resistivity over the range 5–300 K, consistent with formation of a 2D Fermi liquid state. DFT band structure calculations suggest that the ease of metallization of these radicals can be ascribed to their multiorbital character. Mixing and overlap of SOMO- and LUMO-based bands affords an increased kinetic energy stabilization of the metallic state relative to a single SOMO-based band system.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNptkD1PwzAQQC0EoqWwMSOPDE3xR-wmbKiUD4lSBGWOHOcMrtyk2M7Qf0-qFliYTie9eyc9hM4pGVHC6NVS6TASJcmYSA9QnwpGEkGZPER9QghLxpnkPXQSwrJbU5bRY9RjUlBOmeijj8Un4BlE5ZzV-C2qCNjW-Bna6JXDr6qyupuTpq5aHRsfrvGtXUEdbFMrZ-NmiF88hNB6wKqu8Kx10a4d4LkvbWfFU2NAx3CKjoxyAc72c4De76aLyUPyNL9_nNw8JSods5hUkpQkB5mZlKeSKyNLkWupjDBpVWa6ypSiuchLIjjXacUAhKE5N4zrseCUD9Dlzrv2zVcLIRYrGzQ4p2po2lDQMWeiE8isQ4c7VPsmBA-mWHu7Un5TUFJs0xbbtMU-bYdf7M1tuYLqF_5p-fd6e7VsWt8FCv-7vgHwvYJj</recordid><startdate>20151111</startdate><enddate>20151111</enddate><creator>Tian, Di</creator><creator>Winter, Stephen M</creator><creator>Mailman, Aaron</creator><creator>Wong, Joanne W. L</creator><creator>Yong, Wenjun</creator><creator>Yamaguchi, Hiroshi</creator><creator>Jia, Yating</creator><creator>Tse, John S</creator><creator>Desgreniers, Serge</creator><creator>Secco, Richard A</creator><creator>Julian, Stephen R</creator><creator>Jin, Changqing</creator><creator>Mito, Masaki</creator><creator>Ohishi, Yasuo</creator><creator>Oakley, Richard T</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20151111</creationdate><title>The Metallic State in Neutral Radical Conductors: Dimensionality, Pressure and Multiple Orbital Effects</title><author>Tian, Di ; Winter, Stephen M ; Mailman, Aaron ; Wong, Joanne W. L ; Yong, Wenjun ; Yamaguchi, Hiroshi ; Jia, Yating ; Tse, John S ; Desgreniers, Serge ; Secco, Richard A ; Julian, Stephen R ; Jin, Changqing ; Mito, Masaki ; Ohishi, Yasuo ; Oakley, Richard T</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a472t-d60b09e68f43463af6b59c6af5f4db8cd8aa1959b0533c4d2ee5f193f23c75313</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tian, Di</creatorcontrib><creatorcontrib>Winter, Stephen M</creatorcontrib><creatorcontrib>Mailman, Aaron</creatorcontrib><creatorcontrib>Wong, Joanne W. L</creatorcontrib><creatorcontrib>Yong, Wenjun</creatorcontrib><creatorcontrib>Yamaguchi, Hiroshi</creatorcontrib><creatorcontrib>Jia, Yating</creatorcontrib><creatorcontrib>Tse, John S</creatorcontrib><creatorcontrib>Desgreniers, Serge</creatorcontrib><creatorcontrib>Secco, Richard A</creatorcontrib><creatorcontrib>Julian, Stephen R</creatorcontrib><creatorcontrib>Jin, Changqing</creatorcontrib><creatorcontrib>Mito, Masaki</creatorcontrib><creatorcontrib>Ohishi, Yasuo</creatorcontrib><creatorcontrib>Oakley, Richard T</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tian, Di</au><au>Winter, Stephen M</au><au>Mailman, Aaron</au><au>Wong, Joanne W. L</au><au>Yong, Wenjun</au><au>Yamaguchi, Hiroshi</au><au>Jia, Yating</au><au>Tse, John S</au><au>Desgreniers, Serge</au><au>Secco, Richard A</au><au>Julian, Stephen R</au><au>Jin, Changqing</au><au>Mito, Masaki</au><au>Ohishi, Yasuo</au><au>Oakley, Richard T</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The Metallic State in Neutral Radical Conductors: Dimensionality, Pressure and Multiple Orbital Effects</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2015-11-11</date><risdate>2015</risdate><volume>137</volume><issue>44</issue><spage>14136</spage><epage>14148</epage><pages>14136-14148</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Pressure-induced changes in the solid-state structures and transport properties of three oxobenzene-bridged bisdithiazolyl radicals 2 (R = H, F, Ph) over the range 0–15 GPa are described. All three materials experience compression of their π-stacked architecture, be it (i) 1D ABABAB π-stack (R = Ph), (ii) quasi-1D slipped π-stack (R = H), or (iii) 2D brick-wall π-stack (R = F). While R = H undergoes two structural phase transitions, neither of R = F, Ph display any phase change. All three radicals order as spin-canted antiferromagnets, but spin-canted ordering is lost at pressures &lt;1.5 GPa. At room temperature, their electrical conductivity increases rapidly with pressure, and the thermal activation energy for conduction E act is eliminated at pressures ranging from ∼3 GPa for R = F to ∼12 GPa for R = Ph, heralding formation of a highly correlated (or bad) metallic state. For R = F, H the pressure-induced Mott insulator to metal conversion has been tracked by measurements of optical conductivity at ambient temperature and electrical resistivity at low temperature. For R = F compression to 6.2 GPa leads to a quasiquadratic temperature dependence of the resistivity over the range 5–300 K, consistent with formation of a 2D Fermi liquid state. DFT band structure calculations suggest that the ease of metallization of these radicals can be ascribed to their multiorbital character. Mixing and overlap of SOMO- and LUMO-based bands affords an increased kinetic energy stabilization of the metallic state relative to a single SOMO-based band system.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>26513125</pmid><doi>10.1021/jacs.5b08254</doi><tpages>13</tpages><oa>free_for_read</oa></addata></record>
fulltext fulltext
identifier ISSN: 0002-7863
ispartof Journal of the American Chemical Society, 2015-11, Vol.137 (44), p.14136-14148
issn 0002-7863
1520-5126
language eng
recordid cdi_proquest_miscellaneous_1732595968
source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
title The Metallic State in Neutral Radical Conductors: Dimensionality, Pressure and Multiple Orbital Effects
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-19T15%3A27%3A23IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=The%20Metallic%20State%20in%20Neutral%20Radical%20Conductors:%20Dimensionality,%20Pressure%20and%20Multiple%20Orbital%20Effects&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Tian,%20Di&rft.date=2015-11-11&rft.volume=137&rft.issue=44&rft.spage=14136&rft.epage=14148&rft.pages=14136-14148&rft.issn=0002-7863&rft.eissn=1520-5126&rft_id=info:doi/10.1021/jacs.5b08254&rft_dat=%3Cproquest_cross%3E1732595968%3C/proquest_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a472t-d60b09e68f43463af6b59c6af5f4db8cd8aa1959b0533c4d2ee5f193f23c75313%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=1732595968&rft_id=info:pmid/26513125&rfr_iscdi=true