{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,4]],"date-time":"2026-10-04T22:47:27Z","timestamp":1791154047517,"version":"4.1.0"},"reference-count":41,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2012,8,7]],"date-time":"2012-08-07T00:00:00Z","timestamp":1344297600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2012,10,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Nitrogen hyperfine coupling constants (hcc) <jats:italic>a<\/jats:italic><jats:sub>N<\/jats:sub> of nitroxides measured by electron paramagnetic resonance are used to probe the cybotactic effect of solvents. A few articles (Janzen et al., <jats:italic>Can. J. Chem.<\/jats:italic> in <jats:bold>1982<\/jats:bold> for <jats:italic>a<\/jats:italic><jats:sub>H\u03b2<\/jats:sub> and Deng et al., <jats:italic>J. Fluorine Chem.<\/jats:italic> in <jats:bold>2002<\/jats:bold>, both for <jats:italic>a<\/jats:italic><jats:sub>H\u03b2<\/jats:sub> and <jats:italic>a<\/jats:italic><jats:sub>F\u03b2<\/jats:sub>) dealt with the cybotactic effect on the hcc of atoms (hydrogen H, fluorine F, and phosphorus P) in \u03b2 positions of nitroxides. They show either no significant change or an increase in <jats:italic>a<\/jats:italic><jats:sub>\u03b2<\/jats:sub> with <jats:italic>a<\/jats:italic><jats:sub>N<\/jats:sub>. However, an early report by Il\u2032Yasov et al. (<jats:italic>Theor. Exp. Chem.<\/jats:italic> <jats:bold>1976<\/jats:bold>, 656) described a dramatic change in <jats:italic>a<\/jats:italic><jats:sub>P\u03b2<\/jats:sub> with the solvent and an anti\u2010correlation of <jats:italic>a<\/jats:italic><jats:sub>P\u03b2<\/jats:sub> with <jats:italic>a<\/jats:italic><jats:sub>N<\/jats:sub>. We decided to reinvestigate that work using the <jats:italic>N<\/jats:italic>\u2010(2\u2010methylpropyl)\u2010<jats:italic>N<\/jats:italic>\u2010(1\u2010diethylphosphono\u20102,2\u2010dimethylpropyl)\u2010<jats:italic>N<\/jats:italic>\u2010oxyl radical that carries both hydrogen and phosphorus atoms on the same carbon attached to the nitroxy moiety and that is highly persistent, in contrast to the nitroxide used by Il\u2032Yasov. We observe the same trends as those observed by Il\u2032Yasov, except that the solvent cybotactic effect on <jats:italic>a<\/jats:italic><jats:sub>N<\/jats:sub> and <jats:italic>a<\/jats:italic><jats:sub>P\u03b2<\/jats:sub> is dramatically weaker in our case. We showed that <jats:italic>a<\/jats:italic><jats:sub>P\u03b2<\/jats:sub> is correlated to both the cohesive pressure <jats:italic>c<\/jats:italic> and the normalized Reichardt polar constant <jats:italic>E<\/jats:italic><jats:sub>T<\/jats:sub><jats:sup>N<\/jats:sup>, and that hydrogen\u2010bonding donor solvents exhibit a specific behavior.<\/jats:p>","DOI":"10.1002\/cphc.201200420","type":"journal-article","created":{"date-parts":[[2012,8,7]],"date-time":"2012-08-07T15:27:36Z","timestamp":1344353256000},"page":"3542-3548","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Hyperfine Coupling Constants of \u03b2\u2010Phosphorylated Nitroxides: A Tool to Probe the Cybotactic Effect by Electron Paramagnetic Resonance"],"prefix":"10.1002","volume":"13","author":[{"given":"G\u00e9rard","family":"Audran","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paul","family":"Br\u00e9mond","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sylvain R. A.","family":"Marque","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Germain","family":"Obame","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2012,8,7]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527621743"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470666975.ch5"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201102539"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201102539"},{"key":"e_1_2_6_4_2","volume-title":"Assessing Structures and Conformations of Intrinsically Disordered Proteins","author":"Belle V.","year":"2009"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200805321"},{"key":"e_1_2_6_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200805321"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/B418707E"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/op900059x"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0cs00110d"},{"key":"e_1_2_6_9_2","first-page":"1813","volume-title":"Nitroxide\u2010Mediated Polymerization and its Applications in Encyclopedia of Radicals in Chemistry, Biology and Materials","author":"Marque S.","year":"2012"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1371\/journal.pone.0005244"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/cmmi.464"},{"key":"e_1_2_6_12_2","unstructured":"As quoted by Reichardt (ref. [13]) : \u201cA cybotactic region may be defined as the volume around a solute molecule in which the ordering of the solvent molecules has been influenced by the solute including both the first solvation shell and the transition region.\u201d See ref. [14]."},{"key":"e_1_2_6_13_2","volume-title":"Solvent and Solvent Effect in Organic Chemistry, 4th ed.","author":"Reichardt C.","year":"2011"},{"key":"e_1_2_6_14_2","volume-title":"An Introduction to Physical Organic Chemistry","author":"Kosower E. M.","year":"1968"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00431a010"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00039a005"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/mrc.1260251014"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100213a025"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1139\/v82-392"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-1139(02)00074-X"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF01001713"},{"key":"e_1_2_6_21_3","first-page":"831","volume":"12","author":"Mukhtarov A. Sh.","year":"1976","journal-title":"Teor. Eksp. Khim."},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja984013c"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/bk-2006-0944.ch023"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/mren.200900087"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma9918452"},{"key":"e_1_2_6_26_2","unstructured":"For4\u2032 the (EtO)2P(O) group was replaced by (PhO)2P(O) group aP \u03b2dropped from 45.9 G in methylcyclopentane to 18.8 G in MeOH."},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo300459z"},{"key":"e_1_2_6_28_2","unstructured":"\u03a9 and Z constants were tested and good correlations were observed withaN as expected."},{"key":"e_1_2_6_29_2","unstructured":"Correlation was also performed with the data available for2:aN 4=\u22120.97(125)+1.02(8)\u2009aN 2 R2=0.977 N=10."},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/3527601627"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108270198005216"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol2031075"},{"key":"e_1_2_6_33_2","volume-title":"The Properties of Solvents, Vol. 4","author":"Marcus Y.","year":"1998"},{"key":"e_1_2_6_34_2","volume-title":"March\u2019s Advanced Organic Chemistry: Reaction, Mechanism, and Structure, 6th ed.","author":"March J.","year":"2011"},{"key":"e_1_2_6_35_2","unstructured":"Errors are on average \u00b10.06 for all hyperfine coupling constants and are of the size of the symbols in Figure 4."},{"key":"e_1_2_6_36_2","unstructured":"Misreported data cannot be discarded."},{"key":"e_1_2_6_37_2","unstructured":"CCl4and EG were not recorded for5and4 respectively."},{"key":"e_1_2_6_38_2","unstructured":"Cohesive pressure of 25 (TEG) is not available."}],"container-title":["ChemPhysChem"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fcphc.201200420","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cphc.201200420","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T14:37:06Z","timestamp":1760366226000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/cphc.201200420"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2012,8,7]]},"references-count":41,"journal-issue":{"issue":"15","published-print":{"date-parts":[[2012,10,22]]}},"alternative-id":["10.1002\/cphc.201200420"],"URL":"https:\/\/doi.org\/10.1002\/cphc.201200420","archive":["Portico"],"relation":{},"ISSN":["1439-4235","1439-7641"],"issn-type":[{"value":"1439-4235","type":"print"},{"value":"1439-7641","type":"electronic"}],"subject":[],"published":{"date-parts":[[2012,8,7]]},"assertion":[{"value":"2012-05-24","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2012-08-07","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}