Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases:  Isomeric 1,3,5-Tris(naphthyl)benzenes

1,3,5-Tris(1-naphthyl)benzene (1), 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2), and 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene (3) easily supercool and form glasses on cooling from the melt. We synthesized 1, 2, and 3 using Suzuki's conditions to effect the cross-coupling reactions of 1,3,5-tr...

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Published in:Journal of physical chemistry (1952) 1996-01, Vol.100 (3), p.1081-1090
Main Authors: Whitaker, Craig M, McMahon, Robert J
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Language:English
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description 1,3,5-Tris(1-naphthyl)benzene (1), 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2), and 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene (3) easily supercool and form glasses on cooling from the melt. We synthesized 1, 2, and 3 using Suzuki's conditions to effect the cross-coupling reactions of 1,3,5-tribromobenzene with 1-naphthylboronic acid and/or 2-naphthylboronic acid. Variable-temperature 13C NMR studies of 1 establish a barrier of ca. 12 kcal/mol for rotation about the aryl−aryl bond; this value displays good agreement with the barrier of 13 kcal/mol computed using molecular mechanics calculations (MM2). This relatively low rotational barrier is inconsistent with the previously held notion that 1,3,5-tris(1-naphthyl)benzene (1) exists as a mixture of noninterconverting rotational isomers (atropisomers) in solution at room temperature. Variable-temperature 13C NMR studies of 2 establish barriers of ca. 12 kcal/mol for rotation about the 1-naphthyl−aryl bond and
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We synthesized 1, 2, and 3 using Suzuki's conditions to effect the cross-coupling reactions of 1,3,5-tribromobenzene with 1-naphthylboronic acid and/or 2-naphthylboronic acid. Variable-temperature 13C NMR studies of 1 establish a barrier of ca. 12 kcal/mol for rotation about the aryl−aryl bond; this value displays good agreement with the barrier of 13 kcal/mol computed using molecular mechanics calculations (MM2). This relatively low rotational barrier is inconsistent with the previously held notion that 1,3,5-tris(1-naphthyl)benzene (1) exists as a mixture of noninterconverting rotational isomers (atropisomers) in solution at room temperature. Variable-temperature 13C NMR studies of 2 establish barriers of ca. 12 kcal/mol for rotation about the 1-naphthyl−aryl bond and &lt;9 kcal/mol for rotation about the 2-naphthyl−aryl bond. Again, these values display good agreement with the barriers of 14 and 2 kcal/mol computed using molecular mechanics calculations (MM2). Earlier syntheses of 1,3,5-tris(1-naphthyl)benzene (1) provided materials that were poorly characterized by modern standards. 1H and 13C NMR spectra of one such material, a sample widely used in studies of glasses and supercooled liquids, establish the structure of the material as 2, not 1. This revised structural assignment necessitates a re-evaluation of the earlier literature. Differential scanning calorimetry (DSC) establishes that tris(naphthyl)benzenes 1, 2, and 3 melt (T m = 182, 194, and 147 °C, respectively) and form glasses upon cooling (T g = 81, 77, and 67 °C, respectively). Given its low melting point and glass transition temperature, 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene (3) is an attractive candidate for future studies of molecular dynamics of glassy materials.</description><identifier>ISSN: 0022-3654</identifier><identifier>EISSN: 1541-5740</identifier><identifier>DOI: 10.1021/jp9529329</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Journal of physical chemistry (1952), 1996-01, Vol.100 (3), p.1081-1090</ispartof><rights>Copyright © 1996 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a297t-ae693092e35934603393b1c9345cc39805e9e62bffb8e6965c43af4f90907f9b3</citedby><cites>FETCH-LOGICAL-a297t-ae693092e35934603393b1c9345cc39805e9e62bffb8e6965c43af4f90907f9b3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jp9529329$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jp9529329$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,27064,27924,27925,56766,56816</link.rule.ids></links><search><creatorcontrib>Whitaker, Craig M</creatorcontrib><creatorcontrib>McMahon, Robert J</creatorcontrib><title>Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases:  Isomeric 1,3,5-Tris(naphthyl)benzenes</title><title>Journal of physical chemistry (1952)</title><addtitle>J. Phys. Chem</addtitle><description>1,3,5-Tris(1-naphthyl)benzene (1), 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2), and 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene (3) easily supercool and form glasses on cooling from the melt. We synthesized 1, 2, and 3 using Suzuki's conditions to effect the cross-coupling reactions of 1,3,5-tribromobenzene with 1-naphthylboronic acid and/or 2-naphthylboronic acid. Variable-temperature 13C NMR studies of 1 establish a barrier of ca. 12 kcal/mol for rotation about the aryl−aryl bond; this value displays good agreement with the barrier of 13 kcal/mol computed using molecular mechanics calculations (MM2). This relatively low rotational barrier is inconsistent with the previously held notion that 1,3,5-tris(1-naphthyl)benzene (1) exists as a mixture of noninterconverting rotational isomers (atropisomers) in solution at room temperature. Variable-temperature 13C NMR studies of 2 establish barriers of ca. 12 kcal/mol for rotation about the 1-naphthyl−aryl bond and &lt;9 kcal/mol for rotation about the 2-naphthyl−aryl bond. Again, these values display good agreement with the barriers of 14 and 2 kcal/mol computed using molecular mechanics calculations (MM2). Earlier syntheses of 1,3,5-tris(1-naphthyl)benzene (1) provided materials that were poorly characterized by modern standards. 1H and 13C NMR spectra of one such material, a sample widely used in studies of glasses and supercooled liquids, establish the structure of the material as 2, not 1. This revised structural assignment necessitates a re-evaluation of the earlier literature. Differential scanning calorimetry (DSC) establishes that tris(naphthyl)benzenes 1, 2, and 3 melt (T m = 182, 194, and 147 °C, respectively) and form glasses upon cooling (T g = 81, 77, and 67 °C, respectively). Given its low melting point and glass transition temperature, 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene (3) is an attractive candidate for future studies of molecular dynamics of glassy materials.</description><issn>0022-3654</issn><issn>1541-5740</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1996</creationdate><recordtype>article</recordtype><recordid>eNptkM9O20AQh1eolUjTHniDvSAVKYZdr9fO9oasNiCFP1LSqrfVejPGG5x12HEA58SVp-Dd-iQ1pOLU0_w0-vSN5kfIAWfHnMX8ZLlWMlYiVntkwGXCI5kl7AMZMBbHkUhlsk8-IS4ZY1wIPiAvs863FaBDavyC5pUJxrYQ3Na0rvG0KelVuDHeWXphXvemRvrg2ormjb8H78C3dUdPrQVEV9RAZ5s1BNs0NSzo1N1t3OLNPKkNYkevK4OA3_48PdNzbFa90FI-EiMZzYPDr96sq7bq6qMC_BY84GfysexPwpd_c0h-_vg-z8-i6dXkPD-dRiZWWRsZSJVgKgYhlUhSJoQSBbd9ltYKNWYSFKRxUZbFuEdTaRNhyqRUTLGsVIUYkqOd14YGMUCp18GtTOg0Z_q1Wf3ebM9GO9ZhC4_voAm3Os1EJvX8eqZzmc2yya_f-rLnD3e8saiXzSb4_pP_eP8CjjyJjA</recordid><startdate>19960118</startdate><enddate>19960118</enddate><creator>Whitaker, Craig M</creator><creator>McMahon, Robert J</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19960118</creationdate><title>Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases:  Isomeric 1,3,5-Tris(naphthyl)benzenes</title><author>Whitaker, Craig M ; McMahon, Robert J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a297t-ae693092e35934603393b1c9345cc39805e9e62bffb8e6965c43af4f90907f9b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1996</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Whitaker, Craig M</creatorcontrib><creatorcontrib>McMahon, Robert J</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Journal of physical chemistry (1952)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Whitaker, Craig M</au><au>McMahon, Robert J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases:  Isomeric 1,3,5-Tris(naphthyl)benzenes</atitle><jtitle>Journal of physical chemistry (1952)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1996-01-18</date><risdate>1996</risdate><volume>100</volume><issue>3</issue><spage>1081</spage><epage>1090</epage><pages>1081-1090</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><abstract>1,3,5-Tris(1-naphthyl)benzene (1), 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2), and 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene (3) easily supercool and form glasses on cooling from the melt. We synthesized 1, 2, and 3 using Suzuki's conditions to effect the cross-coupling reactions of 1,3,5-tribromobenzene with 1-naphthylboronic acid and/or 2-naphthylboronic acid. Variable-temperature 13C NMR studies of 1 establish a barrier of ca. 12 kcal/mol for rotation about the aryl−aryl bond; this value displays good agreement with the barrier of 13 kcal/mol computed using molecular mechanics calculations (MM2). This relatively low rotational barrier is inconsistent with the previously held notion that 1,3,5-tris(1-naphthyl)benzene (1) exists as a mixture of noninterconverting rotational isomers (atropisomers) in solution at room temperature. Variable-temperature 13C NMR studies of 2 establish barriers of ca. 12 kcal/mol for rotation about the 1-naphthyl−aryl bond and &lt;9 kcal/mol for rotation about the 2-naphthyl−aryl bond. Again, these values display good agreement with the barriers of 14 and 2 kcal/mol computed using molecular mechanics calculations (MM2). Earlier syntheses of 1,3,5-tris(1-naphthyl)benzene (1) provided materials that were poorly characterized by modern standards. 1H and 13C NMR spectra of one such material, a sample widely used in studies of glasses and supercooled liquids, establish the structure of the material as 2, not 1. This revised structural assignment necessitates a re-evaluation of the earlier literature. Differential scanning calorimetry (DSC) establishes that tris(naphthyl)benzenes 1, 2, and 3 melt (T m = 182, 194, and 147 °C, respectively) and form glasses upon cooling (T g = 81, 77, and 67 °C, respectively). Given its low melting point and glass transition temperature, 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene (3) is an attractive candidate for future studies of molecular dynamics of glassy materials.</abstract><pub>American Chemical Society</pub><doi>10.1021/jp9529329</doi><tpages>10</tpages></addata></record>
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title Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases:  Isomeric 1,3,5-Tris(naphthyl)benzenes
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