{"id":"https://openalex.org/W2047475259","doi":"https://doi.org/10.1021/jo020084p","title":"DFT Study of Substituted and Benzannelated Aryl Cations: Substituent Dependency of Singlet/Triplet Ratio1a","display_name":"DFT Study of Substituted and Benzannelated Aryl Cations: Substituent Dependency of Singlet/Triplet Ratio1a","publication_year":2002,"publication_date":"2002-04-10","ids":{"openalex":"https://openalex.org/W2047475259","doi":"https://doi.org/10.1021/jo020084p","mag":"2047475259","pmid":"https://pubmed.ncbi.nlm.nih.gov/11975546"},"language":"en","primary_location":{"id":"doi:10.1021/jo020084p","doi":"https://doi.org/10.1021/jo020084p","is_oa":false,"landing_page_url":"https://doi.org/10.1021/jo020084p","pdf_url":null,"source":{"id":"https://openalex.org/S205050996","display_name":"The Journal of Organic Chemistry","issn_l":"0022-3263","issn":["0022-3263","1520-6904"],"is_oa":false,"is_in_doaj":false,"is_core":true,"listed_in":["cwts-core","dongbi-a","jufo-2","ki-jl-2","medline","norway-2","poland-140","russia-white-list-1","vabb-shw"],"host_organization":"https://openalex.org/P4310320006","host_organization_name":"American Chemical Society","host_organization_lineage":["https://openalex.org/P4310320006"],"host_organization_lineage_names":["American Chemical Society"],"type":"journal"},"license":null,"license_id":null,"version":"publishedVersion","is_accepted":true,"is_published":true,"raw_source_name":"The Journal of Organic Chemistry","raw_type":"journal-article"},"volume":null,"type":"article","indexed_in":["crossref","pubmed"],"open_access":{"is_oa":false,"oa_status":"closed","oa_url":null,"any_repository_has_fulltext":false},"authorships":[{"author_position":"first","author":{"id":"https://openalex.org/A5040503085","display_name":"Kenneth Khosrow Laali","orcid":"https://orcid.org/0000-0002-0294-844X","observed_orcids":["https://orcid.org/0000-0002-0294-844X"]},"institutions":[{"id":"https://openalex.org/I1174212","display_name":"University of Southern California","ror":"https://ror.org/03taz7m60","country_code":"US","type":"education","lineage":["https://openalex.org/I1174212"]}],"countries":["US"],"is_corresponding":false,"raw_author_name":"Kenneth K. Laali","raw_affiliation_strings":["Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661","Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California--University Park, Los Angeles, California 90089-1661, USA"],"raw_orcid":null,"affiliations":[{"raw_affiliation_string":"Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661","institution_ids":["https://openalex.org/I1174212"]},{"raw_affiliation_string":"Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California--University Park, Los Angeles, California 90089-1661, USA","institution_ids":["https://openalex.org/I1174212"]}]},{"author_position":"middle","author":{"id":"https://openalex.org/A5052623513","display_name":"Golam Rasul","orcid":null,"observed_orcids":[]},"institutions":[{"id":"https://openalex.org/I1174212","display_name":"University of Southern California","ror":"https://ror.org/03taz7m60","country_code":"US","type":"education","lineage":["https://openalex.org/I1174212"]}],"countries":["US"],"is_corresponding":false,"raw_author_name":"Golam Rasul","raw_affiliation_strings":["Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661"],"raw_orcid":null,"affiliations":[{"raw_affiliation_string":"Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661","institution_ids":["https://openalex.org/I1174212"]}]},{"author_position":"middle","author":{"id":"https://openalex.org/A5047158225","display_name":"G. K. Surya Prakash","orcid":"https://orcid.org/0000-0002-6350-8325","observed_orcids":["https://orcid.org/0000-0002-6350-8325"]},"institutions":[{"id":"https://openalex.org/I1174212","display_name":"University of Southern California","ror":"https://ror.org/03taz7m60","country_code":"US","type":"education","lineage":["https://openalex.org/I1174212"]}],"countries":["US"],"is_corresponding":false,"raw_author_name":"G. K. Surya Prakash","raw_affiliation_strings":["Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661"],"raw_orcid":null,"affiliations":[{"raw_affiliation_string":"Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661","institution_ids":["https://openalex.org/I1174212"]}]},{"author_position":"last","author":{"id":"https://openalex.org/A5071446330","display_name":"George Andrew Olah","orcid":"https://orcid.org/0000-0002-1788-9753","observed_orcids":["https://orcid.org/0000-0002-1788-9753"]},"institutions":[{"id":"https://openalex.org/I1174212","display_name":"University of Southern California","ror":"https://ror.org/03taz7m60","country_code":"US","type":"education","lineage":["https://openalex.org/I1174212"]}],"countries":["US"],"is_corresponding":false,"raw_author_name":"George A. Olah","raw_affiliation_strings":["Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661"],"raw_orcid":null,"affiliations":[{"raw_affiliation_string":"Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661","institution_ids":["https://openalex.org/I1174212"]}]}],"institutions":[],"countries_distinct_count":1,"institutions_distinct_count":1,"corresponding_author_ids":[],"corresponding_institution_ids":["https://openalex.org/I1174212"],"apc_list":{"value":4500,"currency":"USD","value_usd":4500},"apc_paid":null,"fwci":0.9811,"has_fulltext":false,"cited_by_count":45,"citation_normalized_percentile":{"value":0.70627518,"is_in_top_1_percent":false,"is_in_top_10_percent":false},"cited_by_percentile_year":{"min":89,"max":98},"biblio":{"volume":"67","issue":"9","first_page":"2913","last_page":"2918"},"is_retracted":false,"is_paratext":false,"is_xpac":false,"primary_topic":{"id":"https://openalex.org/T11298","display_name":"Synthesis and Properties of Aromatic Compounds","score":0.4871000051498413,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},"topics":[{"id":"https://openalex.org/T11298","display_name":"Synthesis and Properties of Aromatic Compounds","score":0.4871000051498413,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},{"id":"https://openalex.org/T10002","display_name":"Advanced Chemical Physics Studies","score":0.2304999977350235,"subfield":{"id":"https://openalex.org/subfields/3107","display_name":"Atomic and Molecular Physics, and Optics"},"field":{"id":"https://openalex.org/fields/31","display_name":"Physics and Astronomy"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},{"id":"https://openalex.org/T12191","display_name":"Chemical Reaction Mechanisms","score":0.051500000059604645,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}}],"keywords":[{"id":"https://openalex.org/keywords/aryl-cations","display_name":"aryl cations","score":0.9700000286102295},{"id":"https://openalex.org/keywords/phenyl-cation","display_name":"phenyl cation","score":0.890999972820282},{"id":"https://openalex.org/keywords/singlet-triplet-energy-gap","display_name":"singlet-triplet energy gap","score":0.8849999904632568},{"id":"https://openalex.org/keywords/substituent-effects","display_name":"substituent effects","score":0.8889999985694885},{"id":"https://openalex.org/keywords/nbo-charges","display_name":"NBO charges","score":0.5979999899864197},{"id":"https://openalex.org/keywords/dediazoniation","display_name":"dediazoniation","score":0.8259999752044678},{"id":"https://openalex.org/keywords/decarbonylation","display_name":"decarbonylation","score":0.9490000009536743}],"concepts":[{"id":"https://openalex.org/C33062035","wikidata":"https://www.wikidata.org/wiki/Q3296863","display_name":"Singlet state","level":3,"score":0.8667202591896057},{"id":"https://openalex.org/C2778689049","wikidata":"https://www.wikidata.org/wiki/Q898422","display_name":"Substituent","level":2,"score":0.841119647026062},{"id":"https://openalex.org/C185592680","wikidata":"https://www.wikidata.org/wiki/Q2329","display_name":"Chemistry","level":0,"score":0.8281829357147217},{"id":"https://openalex.org/C30095370","wikidata":"https://www.wikidata.org/wiki/Q899488","display_name":"Protonation","level":3,"score":0.7652479410171509},{"id":"https://openalex.org/C76766466","wikidata":"https://www.wikidata.org/wiki/Q3036629","display_name":"Triplet state","level":3,"score":0.7128652334213257},{"id":"https://openalex.org/C2781076698","wikidata":"https://www.wikidata.org/wiki/Q718074","display_name":"Aryl","level":3,"score":0.6133150458335876},{"id":"https://openalex.org/C20950531","wikidata":"https://www.wikidata.org/wiki/Q161940","display_name":"Heteroatom","level":3,"score":0.5488409399986267},{"id":"https://openalex.org/C152365726","wikidata":"https://www.wikidata.org/wiki/Q1048589","display_name":"Density functional theory","level":2,"score":0.5243306756019592},{"id":"https://openalex.org/C75473681","wikidata":"https://www.wikidata.org/wiki/Q188651","display_name":"Photochemistry","level":1,"score":0.4523906409740448},{"id":"https://openalex.org/C2775859925","wikidata":"https://www.wikidata.org/wiki/Q279525","display_name":"Onium","level":3,"score":0.4410167336463928},{"id":"https://openalex.org/C69523127","wikidata":"https://www.wikidata.org/wiki/Q4480008","display_name":"Ground state","level":2,"score":0.41579577326774597},{"id":"https://openalex.org/C8010536","wikidata":"https://www.wikidata.org/wiki/Q160398","display_name":"Crystallography","level":1,"score":0.35468950867652893},{"id":"https://openalex.org/C155647269","wikidata":"https://www.wikidata.org/wiki/Q243455","display_name":"Medicinal chemistry","level":1,"score":0.31808000802993774},{"id":"https://openalex.org/C147597530","wikidata":"https://www.wikidata.org/wiki/Q369472","display_name":"Computational chemistry","level":1,"score":0.2865808606147766},{"id":"https://openalex.org/C32909587","wikidata":"https://www.wikidata.org/wiki/Q11369","display_name":"Molecule","level":2,"score":0.2134913206100464},{"id":"https://openalex.org/C145148216","wikidata":"https://www.wikidata.org/wiki/Q36496","display_name":"Ion","level":2,"score":0.18710845708847046},{"id":"https://openalex.org/C2780378348","wikidata":"https://www.wikidata.org/wiki/Q25351438","display_name":"Ring (chemistry)","level":2,"score":0.0969361960887909},{"id":"https://openalex.org/C181500209","wikidata":"https://www.wikidata.org/wiki/Q215328","display_name":"Excited state","level":2,"score":0.07942646741867065},{"id":"https://openalex.org/C178790620","wikidata":"https://www.wikidata.org/wiki/Q11351","display_name":"Organic chemistry","level":1,"score":0.07866635918617249},{"id":"https://openalex.org/C121332964","wikidata":"https://www.wikidata.org/wiki/Q413","display_name":"Physics","level":0,"score":0.05756044387817383},{"id":"https://openalex.org/C185544564","wikidata":"https://www.wikidata.org/wiki/Q81197","display_name":"Nuclear physics","level":1,"score":0.0},{"id":"https://openalex.org/C62520636","wikidata":"https://www.wikidata.org/wiki/Q944","display_name":"Quantum mechanics","level":1,"score":0.0},{"id":"https://openalex.org/C2780263894","wikidata":"https://www.wikidata.org/wiki/Q335268","display_name":"Alkyl","level":2,"score":0.0}],"mesh":[{"descriptor_ui":"D000588","descriptor_name":"Amines","qualifier_ui":"Q000737","qualifier_name":"chemistry","is_major_topic":false},{"descriptor_ui":"D001555","descriptor_name":"Benzene Derivatives","qualifier_ui":"Q000737","qualifier_name":"chemistry","is_major_topic":true},{"descriptor_ui":"D002412","descriptor_name":"Cations","qualifier_ui":"Q000737","qualifier_name":"chemistry","is_major_topic":true},{"descriptor_ui":"D002627","descriptor_name":"Chemistry, Physical","qualifier_ui":null,"qualifier_name":null,"is_major_topic":false},{"descriptor_ui":"D008956","descriptor_name":"Models, Chemical","qualifier_ui":null,"qualifier_name":null,"is_major_topic":false},{"descriptor_ui":"D008968","descriptor_name":"Molecular Conformation","qualifier_ui":null,"qualifier_name":null,"is_major_topic":false},{"descriptor_ui":"D015394","descriptor_name":"Molecular Structure","qualifier_ui":null,"qualifier_name":null,"is_major_topic":false},{"descriptor_ui":"D055598","descriptor_name":"Chemical Phenomena","qualifier_ui":null,"qualifier_name":null,"is_major_topic":false}],"locations_count":2,"locations":[{"id":"doi:10.1021/jo020084p","doi":"https://doi.org/10.1021/jo020084p","is_oa":false,"landing_page_url":"https://doi.org/10.1021/jo020084p","pdf_url":null,"source":{"id":"https://openalex.org/S205050996","display_name":"The Journal of Organic Chemistry","issn_l":"0022-3263","issn":["0022-3263","1520-6904"],"is_oa":false,"is_in_doaj":false,"is_core":true,"listed_in":["cwts-core","dongbi-a","jufo-2","ki-jl-2","medline","norway-2","poland-140","russia-white-list-1","vabb-shw"],"host_organization":"https://openalex.org/P4310320006","host_organization_name":"American Chemical Society","host_organization_lineage":["https://openalex.org/P4310320006"],"host_organization_lineage_names":["American Chemical Society"],"type":"journal"},"license":null,"license_id":null,"version":"publishedVersion","is_accepted":true,"is_published":true,"raw_source_name":"The Journal of Organic Chemistry","raw_type":"journal-article"},{"id":"pmid:11975546","doi":null,"is_oa":false,"landing_page_url":"https://pubmed.ncbi.nlm.nih.gov/11975546","pdf_url":null,"source":{"id":"https://openalex.org/S4306525036","display_name":"PubMed","issn_l":null,"issn":null,"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":"https://openalex.org/I1299303238","host_organization_name":"National Institutes of Health","host_organization_lineage":["https://openalex.org/I1299303238"],"host_organization_lineage_names":[],"type":"repository"},"license":null,"license_id":null,"version":"publishedVersion","is_accepted":true,"is_published":true,"raw_source_name":"The Journal of organic chemistry","raw_type":"Journal Article"}],"best_oa_location":null,"sustainable_development_goals":[],"study_designs":[],"awards":[],"funders":[],"has_content":{"pdf":false,"grobid_xml":false},"content_urls":null,"referenced_works_count":10,"referenced_works":["https://openalex.org/W1979013145","https://openalex.org/W2038767330","https://openalex.org/W2064811421","https://openalex.org/W2065617724","https://openalex.org/W2069556934","https://openalex.org/W2083861784","https://openalex.org/W2506395849","https://openalex.org/W2951672535","https://openalex.org/W3025953456","https://openalex.org/W4285719527"],"related_works":["https://openalex.org/W2032206668","https://openalex.org/W2013678044","https://openalex.org/W2292155631","https://openalex.org/W1964178367","https://openalex.org/W1994278606","https://openalex.org/W3186858347","https://openalex.org/W1971339875","https://openalex.org/W1608559884","https://openalex.org/W2884999836","https://openalex.org/W2085617237"],"abstract_inverted_index":{"By":[0],"using":[1],"density":[2],"functional":[3],"theory":[4],"(DFT)":[5],"method":[6],"at":[7,194,246],"the":[8,16,19,29,38,46,51,61,77,82,119,125,137,146,156,164,173,176,183,195,198,203,207,213,221,232,240,247,257,277,283],"B3LYP/6-311+G":[9],"level,":[10],"it":[11],"has":[12,149],"been":[13],"shown":[14],"that":[15],"preference":[17],"for":[18,50,113,262],"singlet-state":[20],"phenyl":[21,53],"cation":[22,54,175,269],"can":[23],"be":[24,58],"dramatically":[25],"increased":[26],"relative":[27,120,157,204],"to":[28,57,270,275],"triplet":[30,62,83,160,177,208,222],"state":[31,49,128,223],"by":[32,63],"introducing":[33],"onium":[34],"cationic":[35,248],"substituents":[36],"in":[37,76,100,122,145,172,227,231,273],"para":[39,78,147],"position.":[40],"At":[41],"this":[42],"level":[43],"of":[44,67,106,118,124,159,187,197,206,279,282],"theory,":[45],"singlet":[47,126,184],"ground":[48,127],"parent":[52],"was":[55],"found":[56],"lower":[59,226],"than":[60],"19.6":[64],"kcal/mol.":[65],"Introduction":[66,186],"electron-donating":[68],"substituent":[69,108],"groups,":[70,189],"namely":[71],"-NMe(2),":[72],"-NH(2),":[73],"and":[74,87,134,166,192,237,259,264,267],"-SMe":[75],"position,":[79],"strongly":[80],"favors":[81],"state.":[84,209],"The":[85,142,243],"-OMe":[86],"-SH":[88],"groups":[89,109],"cause":[90],"a":[91,115,150],"similar":[92,151],"but":[93,220],"smaller":[94],"effect,":[95],"whereas":[96],"-OH":[97],"substitution":[98],"results":[99],"an":[101],"energetically":[102,170],"identical":[103],"system.":[104],"Protonation":[105],"these":[107],"form":[110],"onium-phenyl":[111],"dications":[112,234],"which":[114],"complete":[116],"reversal":[117],"stabilities":[121],"favor":[123],"are":[129,169,235],"indicated":[130],"with":[131,239],"-SH(2)(+),":[132],"-SMeH(+),":[133],"-NH(3)(+)":[135],"showing":[136],"largest":[138],"singlet/triplet":[139,214],"energy":[140,215],"difference.":[141],"-N(2)(+)":[143],"group":[144],"position":[148],"effect.":[152],"Benzannelation":[153],"also":[154,251,255],"increases":[155,202],"stability":[158,205],"aryl":[161,271],"cation.":[162],"Whereas":[163],"1-naphththyl":[165],"2-naphthyl":[167],"cations":[168,272],"identical,":[171],"9-anthracenyl":[174],"minimum":[178],"lies":[179],"13.4":[180],"kcal/mol":[181],"below":[182],"minimum.":[185],"activating":[188],"i.e.,":[190],"OH":[191],"NMe(2)":[193],"4-position":[196],"1-naphthyl":[199],"cation,":[200],"greatly":[201],"Upon":[210],"heteroatom":[211],"protonation,":[212],"gap":[216],"is":[217],"substantially":[218],"narrowed":[219],"still":[224],"remains":[225],"energy.":[228],"Structural":[229],"features":[230],"resulting":[233],"discussed":[236],"compared":[238],"corresponding":[241],"monocations.":[242],"NBO":[244],"charges":[245],"centers":[249],"were":[250],"compared.":[252],"We":[253],"have":[254],"calculated":[256],"dediazoniation":[258],"decarbonylation":[260],"energetics":[261],"mono-":[263],"bis-o-trimethylsilyl-substituted":[265],"benzenediazonium":[266],"benzoyl":[268],"order":[274],"probe":[276],"effect":[278],"beta-silyl":[280],"stabilization":[281],"positive":[284],"charge.":[285]},"counts_by_year":[{"year":2026,"cited_by_count":1},{"year":2025,"cited_by_count":1},{"year":2022,"cited_by_count":3},{"year":2020,"cited_by_count":3},{"year":2018,"cited_by_count":1},{"year":2017,"cited_by_count":3},{"year":2016,"cited_by_count":4},{"year":2015,"cited_by_count":1},{"year":2014,"cited_by_count":4},{"year":2013,"cited_by_count":2},{"year":2012,"cited_by_count":4}],"updated_date":"2026-10-31T12:09:11.096373","created_date":"2016-06-24T00:00:00"}
