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H.Organic Chemistry of Stable Free Radicals;Academic Press:London, 1968; Chapter5, pp180\u2212246"},{"key":"ref22\/cit22a","first-page":"2217","volume":"10","author":"Ivanov Y. A.","year":"1976","journal-title":"Izv. Akad. Nauk SSSR, Ser. Khim."},{"key":"ref22\/cit22b","unstructured":"bIn the original synthesis of radical1, the yield of 70% from the corresponding amine, using Na2WO4\/H2O2, was reported, though purity of1was not established."},{"key":"ref23\/cit23","doi-asserted-by":"crossref","first-page":"9341","DOI":"10.1021\/jo0616299","volume":"71","author":"Delen Z.","year":"2006","journal-title":"J. Org. Chem."},{"key":"ref24\/cit24","doi-asserted-by":"crossref","first-page":"581","DOI":"10.1016\/S0379-6779(02)00353-3","volume":"133","author":"Seino M.","year":"2003","journal-title":"Synth. Met."},{"key":"ref25\/cit25","doi-asserted-by":"crossref","first-page":"4238","DOI":"10.1021\/ja00011a028","volume":"113","author":"Ishida T.","year":"1991","journal-title":"J. Am. Chem. 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M., Ed.Marcel Dekker:New York, 1999; pp267\u2212284","DOI":"10.1201\/9780203748503-17"},{"key":"ref31\/cit31","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1021\/jo702151n","volume":"73","author":"Vale M.","year":"2008","journal-title":"J. Org. Chem."},{"key":"ref32\/cit32","doi-asserted-by":"crossref","first-page":"4677","DOI":"10.1016\/S0040-4039(00)80578-X","volume":"29","author":"Murray R. W.","year":"1988","journal-title":"Tetrahedron Lett."},{"key":"ref33\/cit33","unstructured":"As a small correction for bulk paramagnetic susceptibility of the order of 0.5 ppm is not included, the actual value of \u0394\u03b4pis somewhat lower."},{"key":"ref34\/cit34","unstructured":"ForS= 1\/2 nitroxide radical (g= 2.005) at room temperature (T= 295 K):aH(mT) = 0.00133 \u0394\u03b4p."},{"key":"ref35\/cit35a","unstructured":"aThe values ofaH= +0.0054 mT andaH= +0.0059 mT for the protons of thetert-butyl group were obtained from the1H NMR spectra of 4-tert-butylphenyl-tert-butylnitroxide radical in chloroform-dand carbon tetrachloride."},{"key":"ref35\/cit35b","doi-asserted-by":"crossref","first-page":"231","DOI":"10.1002\/jlac.197319730211","author":"Torsell K.","year":"1973","journal-title":"Liebigs Ann. Chem."},{"key":"ref35\/cit35c","doi-asserted-by":"crossref","first-page":"2213","DOI":"10.1039\/p19740002213","author":"Forrester A. R.","year":"1974","journal-title":"J. Chem. Soc., Perkin Trans. I"},{"key":"ref36\/cit36","doi-asserted-by":"crossref","unstructured":"In polyarylmethyl triradical, the1H-resonance at +10 ppm was assigned to thet-Bu groups in the 4-tert-butylphenyls adjacent to the radicals, suggesting analogous homohyperconjugation:Rajca, S. and Rajca, A.J. Am. Chem. Soc.,1995,117,9172\u22129179","DOI":"10.1021\/ja00141a008"},{"key":"ref37\/cit37","doi-asserted-by":"crossref","first-page":"7232","DOI":"10.1021\/ja071881d","volume":"129","author":"Rajca A.","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref38\/cit38","doi-asserted-by":"crossref","first-page":"9014","DOI":"10.1021\/ja052002v","volume":"127","author":"Rajca A.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref39\/cit39","doi-asserted-by":"crossref","first-page":"3724","DOI":"10.1021\/ja01042a006","volume":"91","author":"Calder A.","year":"1969","journal-title":"J. Am. Chem. Soc."},{"key":"ref40\/cit40","doi-asserted-by":"crossref","first-page":"5047","DOI":"10.1039\/b508094k","author":"Spagnol G.","year":"2005","journal-title":"Chem. Commun."},{"key":"ref41\/cit41a","unstructured":"aThe dependence of the spectral width (|2D|) on the inter-dipole distance (r) is calculated according to the following equation: |2D| = 3g\u03b2\/r3= 2.78 \u00d7 103(g\/r3), where |D| is in mT andris in \u00c5."},{"key":"ref41\/cit41b","doi-asserted-by":"crossref","first-page":"6560","DOI":"10.1021\/ja00360a005","volume":"105","author":"Eaton S. S.","year":"1983","journal-title":"J. Am. Chem. Soc."},{"key":"ref42\/cit42","unstructured":"In the spectral simulation of2in Figure 5, it is assumed that the magnetic dipole-dipole inter-spin vector (principal axis of the diradicalD-tensor) is along a principal axis of the nitroxideg- andA-tensor. Out-of-plane distortion in2may misalign the principal axes, and thus the value of \u201c|Ayy\/hc|\u201d with they-axis defined by theD-tensor in the spectral simulation would be lower, underestimating the actual value of |Ayy\/hc| with they-axis parallel to the 2pNorbital axis."},{"key":"ref43\/cit43","doi-asserted-by":"crossref","first-page":"303","DOI":"10.1002\/anie.197203031","volume":"11","author":"Rassat A.","year":"1972","journal-title":"Angew. Chem., Int. Ed. Engl."},{"key":"ref44\/cit44","doi-asserted-by":"crossref","first-page":"2909","DOI":"10.1063\/1.1697233","volume":"43","author":"Griffith O. H.","year":"1965","journal-title":"J. Chem. Phys."},{"key":"ref45\/cit45","doi-asserted-by":"crossref","first-page":"13497","DOI":"10.1021\/ja063567+","volume":"118","author":"Rajca A.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref46\/cit46a","unstructured":"aFor oxidations of diaryldiamine5, the relative EPR signal intensities from double integration of the side bands and the center peaks are about 0.3: 0.7, respectively (Figures S5A and S5C,Supporting Information). Because the side-bands underneath the center peaks could not be integrated and the EPR intensities are related by a factor ofS(S+ 1), the ratio of 0.3: 0.7 is probably not much different from the molar ratio ofS= 1 diradical toS= 1\/2 monoradical. This ratio would give spin-average ofSclose toSs\u2248 0.7, which is in agreement withS= 1\/2 \u2212 1 obtained from the curvature of Brillouin plots (Figure S5B,Supporting Information)."},{"key":"ref46\/cit46b","doi-asserted-by":"crossref","first-page":"6308","DOI":"10.1021\/ja990881d","volume":"121","author":"Rajca A.","year":"1999","journal-title":"J. Am. Chem. Soc."},{"key":"ref47\/cit47","volume-title":"Gaussian 03","author":"Frisch M. J.","year":"2004"},{"key":"ref48\/cit48","unstructured":"Full geometry optimization of the broken-symmetry singlet for2A-antilowers the energy by 0.08 kcal mol\u22121only, thus the singlet geometries of were not optimized. This may introduce an additional, though small, source of overestimate of the singlet-triplet gaps."},{"key":"ref49\/cit49","doi-asserted-by":"crossref","first-page":"12823","DOI":"10.1021\/ja0355067","volume":"125","author":"Zhang D. Y.","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"ref50\/cit50a","doi-asserted-by":"crossref","first-page":"9664","DOI":"10.1021\/jp953697x","volume":"100","author":"Cramer C. J.","year":"1996","journal-title":"J. Phys. Chem."},{"key":"ref50\/cit50b","doi-asserted-by":"crossref","first-page":"10113","DOI":"10.1021\/ja070143m","volume":"129","author":"Winter A. H.","year":"2007","journal-title":"Am. Chem. 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