Stability and Aromaticity of the Cyclopenta-Fused Pyrene Congeners
The aromaticity of all possible cyclopenta-fused pyrene congeners has been investigated at various levels of theory. On the basis of the calculated resonance energies and magnetic properties (δ1H data, magnetic susceptibility anisotropies, and NICS values), the overall aromaticity of these compounds...
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| Veröffentlicht in: | Journal of the American Chemical Society 2002-03, Vol.124 (10), p.2363-2370 |
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| creator | Havenith, Remco W. A Jiao, Haijun Jenneskens, Leonardus W van Lenthe, Joop H Sarobe, Martin Schleyer, Paul von Ragué Kataoka, Masahiro Necula, Atena Scott, Lawrence T |
| description | The aromaticity of all possible cyclopenta-fused pyrene congeners has been investigated at various levels of theory. On the basis of the calculated resonance energies and magnetic properties (δ1H data, magnetic susceptibility anisotropies, and NICS values), the overall aromaticity of these compounds is found to decrease gradually with increasing number of externally fused five-membered rings. The relatively small differences ( dicyclopenta[cd,jk]- > dicyclopenta[cd,mn]pyrene), which differs from the aromaticity order based on the magnetic criteria (dicyclopenta[cd,mn]- > dicyclopenta[cd,fg]- > dicyclopenta[cd,jk]pyrene), is shown by model calculations to be dominated by σ-strain imposed on the pyrene skeleton by sequential cyclopenta-fusion. This is supported by the computed homodesmotic reaction energies and aromatic stabilization energy (ASEisom) from isodesmic aromatic−nonaromatic isomerization, and by the model calculations on “distorted” cyclopenta[cd]pyrenes. The elusive tetracyclopenta[cd,fg,jk,mn]pyrene is computed to be bowl-shaped; its corresponding planar geometry is the transition state for bowl−bowl interconversion. |
| doi_str_mv | 10.1021/ja011538n |
| format | Article |
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A ; Jiao, Haijun ; Jenneskens, Leonardus W ; van Lenthe, Joop H ; Sarobe, Martin ; Schleyer, Paul von Ragué ; Kataoka, Masahiro ; Necula, Atena ; Scott, Lawrence T</creator><creatorcontrib>Havenith, Remco W. A ; Jiao, Haijun ; Jenneskens, Leonardus W ; van Lenthe, Joop H ; Sarobe, Martin ; Schleyer, Paul von Ragué ; Kataoka, Masahiro ; Necula, Atena ; Scott, Lawrence T</creatorcontrib><description>The aromaticity of all possible cyclopenta-fused pyrene congeners has been investigated at various levels of theory. On the basis of the calculated resonance energies and magnetic properties (δ1H data, magnetic susceptibility anisotropies, and NICS values), the overall aromaticity of these compounds is found to decrease gradually with increasing number of externally fused five-membered rings. The relatively small differences (<5 kcal/mol) in thermodynamic stability of the isomeric dicyclopentapyrenes (E tot: dicyclopenta[cd,fg]- > dicyclopenta[cd,jk]- > dicyclopenta[cd,mn]pyrene), which differs from the aromaticity order based on the magnetic criteria (dicyclopenta[cd,mn]- > dicyclopenta[cd,fg]- > dicyclopenta[cd,jk]pyrene), is shown by model calculations to be dominated by σ-strain imposed on the pyrene skeleton by sequential cyclopenta-fusion. This is supported by the computed homodesmotic reaction energies and aromatic stabilization energy (ASEisom) from isodesmic aromatic−nonaromatic isomerization, and by the model calculations on “distorted” cyclopenta[cd]pyrenes. The elusive tetracyclopenta[cd,fg,jk,mn]pyrene is computed to be bowl-shaped; its corresponding planar geometry is the transition state for bowl−bowl interconversion.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja011538n</identifier><identifier>PMID: 11878993</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Atomic and molecular physics ; Electric and magnetic moments (and derivatives), polarizability and magnetic susceptibility ; Exact sciences and technology ; Molecular properties and interactions with photons ; Physics ; Properties of molecules and molecular ions</subject><ispartof>Journal of the American Chemical Society, 2002-03, Vol.124 (10), p.2363-2370</ispartof><rights>Copyright © 2002 American Chemical Society</rights><rights>2002 INIST-CNRS</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a480t-b4e314ff49f3315e5dd92f48cf764bf7507dba5a2030357c8e626985bb6a46633</citedby><cites>FETCH-LOGICAL-a480t-b4e314ff49f3315e5dd92f48cf764bf7507dba5a2030357c8e626985bb6a46633</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/ja011538n$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja011538n$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2763,27074,27922,27923,56736,56786</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=13554595$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11878993$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Havenith, Remco W. A</creatorcontrib><creatorcontrib>Jiao, Haijun</creatorcontrib><creatorcontrib>Jenneskens, Leonardus W</creatorcontrib><creatorcontrib>van Lenthe, Joop H</creatorcontrib><creatorcontrib>Sarobe, Martin</creatorcontrib><creatorcontrib>Schleyer, Paul von Ragué</creatorcontrib><creatorcontrib>Kataoka, Masahiro</creatorcontrib><creatorcontrib>Necula, Atena</creatorcontrib><creatorcontrib>Scott, Lawrence T</creatorcontrib><title>Stability and Aromaticity of the Cyclopenta-Fused Pyrene Congeners</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>The aromaticity of all possible cyclopenta-fused pyrene congeners has been investigated at various levels of theory. On the basis of the calculated resonance energies and magnetic properties (δ1H data, magnetic susceptibility anisotropies, and NICS values), the overall aromaticity of these compounds is found to decrease gradually with increasing number of externally fused five-membered rings. The relatively small differences (<5 kcal/mol) in thermodynamic stability of the isomeric dicyclopentapyrenes (E tot: dicyclopenta[cd,fg]- > dicyclopenta[cd,jk]- > dicyclopenta[cd,mn]pyrene), which differs from the aromaticity order based on the magnetic criteria (dicyclopenta[cd,mn]- > dicyclopenta[cd,fg]- > dicyclopenta[cd,jk]pyrene), is shown by model calculations to be dominated by σ-strain imposed on the pyrene skeleton by sequential cyclopenta-fusion. This is supported by the computed homodesmotic reaction energies and aromatic stabilization energy (ASEisom) from isodesmic aromatic−nonaromatic isomerization, and by the model calculations on “distorted” cyclopenta[cd]pyrenes. The elusive tetracyclopenta[cd,fg,jk,mn]pyrene is computed to be bowl-shaped; its corresponding planar geometry is the transition state for bowl−bowl interconversion.</description><subject>Atomic and molecular physics</subject><subject>Electric and magnetic moments (and derivatives), polarizability and magnetic susceptibility</subject><subject>Exact sciences and technology</subject><subject>Molecular properties and interactions with photons</subject><subject>Physics</subject><subject>Properties of molecules and molecular ions</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2002</creationdate><recordtype>article</recordtype><recordid>eNpt0MtKxDAUBuAgio6XhS8g3Si4qOZ-WergqCgoeFm4Cadpoh077Zi04Ly9lRmcjavDyfn4CT9ChwSfEUzJ-RQwIYLpZgONiKA4F4TKTTTCGNNcacl20G5K02HlVJNttEOIVtoYNkKXTx0UVV11iwyaMruI7Qy6yv3ubci6D5-NF65u577pIJ_0yZfZ4yL6Znhvm_dhxrSPtgLUyR-s5h56mVw9j2_y-4fr2_HFfQ5c4y4vuGeEh8BNYIwIL8rS0MC1C0ryIiiBVVmAAIoZZkI57SWVRouikMClZGwPnSxz57H96n3q7KxKztc1NL7tk1WEG2KYGeDpErrYphR9sPNYzSAuLMH2tzD7V9hgj1ahfTHz5VquGhrA8QpAclCHCI2r0toxIbgwYnD50lWp899_d4ifViqmhH1-fLJ3mOrLNzmxr-tccMlO2z42Q3f_fPAH70yMkA</recordid><startdate>20020313</startdate><enddate>20020313</enddate><creator>Havenith, Remco W. 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A ; Jiao, Haijun ; Jenneskens, Leonardus W ; van Lenthe, Joop H ; Sarobe, Martin ; Schleyer, Paul von Ragué ; Kataoka, Masahiro ; Necula, Atena ; Scott, Lawrence T</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a480t-b4e314ff49f3315e5dd92f48cf764bf7507dba5a2030357c8e626985bb6a46633</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2002</creationdate><topic>Atomic and molecular physics</topic><topic>Electric and magnetic moments (and derivatives), polarizability and magnetic susceptibility</topic><topic>Exact sciences and technology</topic><topic>Molecular properties and interactions with photons</topic><topic>Physics</topic><topic>Properties of molecules and molecular ions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Havenith, Remco W. A</creatorcontrib><creatorcontrib>Jiao, Haijun</creatorcontrib><creatorcontrib>Jenneskens, Leonardus W</creatorcontrib><creatorcontrib>van Lenthe, Joop H</creatorcontrib><creatorcontrib>Sarobe, Martin</creatorcontrib><creatorcontrib>Schleyer, Paul von Ragué</creatorcontrib><creatorcontrib>Kataoka, Masahiro</creatorcontrib><creatorcontrib>Necula, Atena</creatorcontrib><creatorcontrib>Scott, Lawrence T</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><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>Havenith, Remco W. A</au><au>Jiao, Haijun</au><au>Jenneskens, Leonardus W</au><au>van Lenthe, Joop H</au><au>Sarobe, Martin</au><au>Schleyer, Paul von Ragué</au><au>Kataoka, Masahiro</au><au>Necula, Atena</au><au>Scott, Lawrence T</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Stability and Aromaticity of the Cyclopenta-Fused Pyrene Congeners</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2002-03-13</date><risdate>2002</risdate><volume>124</volume><issue>10</issue><spage>2363</spage><epage>2370</epage><pages>2363-2370</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>The aromaticity of all possible cyclopenta-fused pyrene congeners has been investigated at various levels of theory. On the basis of the calculated resonance energies and magnetic properties (δ1H data, magnetic susceptibility anisotropies, and NICS values), the overall aromaticity of these compounds is found to decrease gradually with increasing number of externally fused five-membered rings. The relatively small differences (<5 kcal/mol) in thermodynamic stability of the isomeric dicyclopentapyrenes (E tot: dicyclopenta[cd,fg]- > dicyclopenta[cd,jk]- > dicyclopenta[cd,mn]pyrene), which differs from the aromaticity order based on the magnetic criteria (dicyclopenta[cd,mn]- > dicyclopenta[cd,fg]- > dicyclopenta[cd,jk]pyrene), is shown by model calculations to be dominated by σ-strain imposed on the pyrene skeleton by sequential cyclopenta-fusion. This is supported by the computed homodesmotic reaction energies and aromatic stabilization energy (ASEisom) from isodesmic aromatic−nonaromatic isomerization, and by the model calculations on “distorted” cyclopenta[cd]pyrenes. The elusive tetracyclopenta[cd,fg,jk,mn]pyrene is computed to be bowl-shaped; its corresponding planar geometry is the transition state for bowl−bowl interconversion.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>11878993</pmid><doi>10.1021/ja011538n</doi><tpages>8</tpages><oa>free_for_read</oa></addata></record> |
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| subjects | Atomic and molecular physics Electric and magnetic moments (and derivatives), polarizability and magnetic susceptibility Exact sciences and technology Molecular properties and interactions with photons Physics Properties of molecules and molecular ions |
| title | Stability and Aromaticity of the Cyclopenta-Fused Pyrene Congeners |
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