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High Spin Molecules Directed Towards Molecular Magnets

  • Chapter
EPR of Free Radicals in Solids II

Part of the book series: Progress in Theoretical Chemistry and Physics ((PTCP,volume 25))

Abstract

EPR has often been used to define spin states of high spin molecules. This chapter outlines some meaningful considerations for the classification of interacting radicals and the determination of their ground state spin multiplicity. Then a review on different classes of high spin molecules follows, sorted by their spin state, summarizing the application of EPR in that domain.

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References

  1. Chittapeddi S, Cromack KR, Miller JS, Epstein A (1987) Ferromagnetism in molecular decamethylferrocenium tetracyanoethenide (DMEFC TCNE). Phys Rev Lett 58:2695–2698

    Google Scholar 

  2. Tamura M, Nakazawa Y, Shiomi D, Nozawa K, Hoosokoshi Y, Ishikawa M, Takahashi M Kinoshita M (1991) Bulk ferromagnetism in the beta-phase crystal of the para–nitrophenyl nitronyl nitroxide radical. Chem Phys Lett 186:401–404

    CAS  Google Scholar 

  3. Schlenk W, Brauns M (1915) Some bis-triaryl-methyle [Triarylmethyle XV]. Ber Dtsch Chem Ges 48:716–728

    CAS  Google Scholar 

  4. Tschitschibabin AE (1907) Some phenylate derivates of p, p ditoyl. Ber Dtsch Chem Ges 40:1810–1819

    CAS  Google Scholar 

  5. Yang NC, Castro AJ (1960) Synthesis of a stable biradical. J Am Chem Soc 82:6208–6208

    CAS  Google Scholar 

  6. Coppinger GM (1962) A stable phenoxy radical inert to oxygen. Tetrahedron 18:61–63

    CAS  Google Scholar 

  7. Scheffler K, Stegmann HB (1970) Elektronenspinresonanz. Springer, Heidelberg

    Google Scholar 

  8. Teki Y, Miyamoto S, Iimura K, Nakatsuji M (2000) Intramolecular spin alignment utilizing the excited molecular field between the triplet (S = 1) excited state and the dangling stable radicals (S = 1/2) as studied by time-resolved electron spin resonance: observation of the excited quartet (S = 3/2) and quintet (S = 2) states on the purely organic pi-conjugated spin systems. J Am Chem Soc 122:984–985

    CAS  Google Scholar 

  9. Teki Y, Nakatsuji M, Miura, Y (2002) Excited high spin states of novel pi conjugated verdazyl radicals: photoinduced spin alignment utilizing the excited molecular field. Mol Phys 100:1385–1394

    CAS  Google Scholar 

  10. Takui T (2000) Characterization of molecular magnetism. In: Itoh K, Kinoshita M (eds) Molecular magnetism. Kodansha (Gordon and Breach), Tokyo

    Google Scholar 

  11. Schweiger A, Jeschke G (2001) Principles of pulse electron paramagnetic resonance. Oxford University Press, Oxford

    Google Scholar 

  12. Tomioka H, Hattori M, Hirai K, Sato K, Shiomi D, Takui T, Itoh K (1998) Persistent high-spin polycarbene: generation of polybrominated 1,3,5-tris-2,4-(phenylcarbeno)phenyl ethynyl benzene (S = 3) and spin identification by two-dimensional electron spin transient nutation spectroscopy. J Am Chem Soc 120:1106–1107

    CAS  Google Scholar 

  13. Weil JA, Bolton JR, Wertz JE (1994) Electron paramagnetic resonance. Wiley, New York

    Google Scholar 

  14. Trozzolo AM, Murray RW, Smolinsky G, Yager WA, Wassermann E (1963) EPR of dicarbene and dinitrene derivatives. J Am Chem Soc 85:2526–2527

    CAS  Google Scholar 

  15. Wassermann E, Murray RW, Yager WA, Trozzolo AM, Smolinsky G (1967) Quintet ground states of m-dicarbene and m-dinitrene compounds. J Am Chem Soc 89:5076–5077

    Google Scholar 

  16. Itoh K (1967) Electron spin resonance of an aromatic hydrocarbon in its quintet ground state. Chem Phys Lett 1:235–238

    CAS  Google Scholar 

  17. Teki Y, Takui T, Itoh K (1988) General conditions for the occurrence of off-axis extra lines in powder-pattern electron-spin-resonance fine-structure. J Chem Phys 88:6134–6145

    Google Scholar 

  18. Adam W, Baumgarten M, Maas W (2000) A hydrocarbon hexaradical with three localized 1,3-cyclopentanediyl triplet diradicals linked by 1,3,5-trimethylenebenzene as ferromagnetic coupler: synthesis of the azoalkane precursor, photochemical generation of the polyradical, and EPR characterization of its septet-spin ground state. J Am Chem Soc 122:6735–6738

    CAS  Google Scholar 

  19. Wienk MM, Janssen RAJ (1996) Triplet-state phosphinyl diradicals. Chem Commun 16:1919–1920

    Google Scholar 

  20. Kirste B, vanWilligen H, Kurreck H, Möbius K, Plato M, Biehl R (1978) Endor of organic triplet-state and quartet-state in liquid solutions and in rigid media. J Am Chem Soc 100:7505–7513

    CAS  Google Scholar 

  21. Kurreck H, Kirste B, Lubitz W (1988) Electron nuclear double resonance spectroscopy of radicals in solution. Weinheim

    Google Scholar 

  22. Takui T, Sato K, Shiomi D, Itoh K (1999) Continuous wave ESR and Fourier transform-pulsed electron spin transient nutation spectroscopy. In: Lahti PM (ed) Magnetic properties of organic materials. Marcel Decker, New York

    Google Scholar 

  23. Zoppellaro G, Geies A, Enkelmann V, Baumgarten M (2004) 2,6-Bis(pyrazolyl)pyridine functionalised with two nitronylnitroxide and iminonitroxide radicals. Eur J Org Chem 2367–2374

    Google Scholar 

  24. Bleaney B, Bowers K (1952) Anomalous paramagnetism of copper acetate. Proc. R. Soc., London A214:451–456

    Google Scholar 

  25. Iwamura H (1990) High-spin organic molecules and spin alignment in organic molecular assemblies. Adv Phys Org Chem 26:179–253

    CAS  Google Scholar 

  26. O Kahn (1993) Molecular magnets. VCH, Weinheim

    Google Scholar 

  27. Miller JS, Epstein AJ (1994) Organic and organometallic molecular magnetic materials - designer magnets. Angew Chem 106:399–415

    CAS  Google Scholar 

  28. Lahti PM (1999) Magnetic properties of organic materials. Marcel Decker, New York

    Google Scholar 

  29. Itoh K, Kinoshita M (2000) Molecular magnetism. Kodansha (Gordon and Breach), Tokyo

    Google Scholar 

  30. Miller JS, Drillon M (2001–2003) Magnetism, molecules to materials, vols I–IV. Wiley-VCH

    Google Scholar 

  31. Veciana J (2001) π-Electron magnetism. From molecules to materials. Structure & bonding Vol 100., Springer

    Google Scholar 

  32. Rajca A (1994) Organic diradicals and polyradicals – from spin coupling to magnetism Chem Rev 94:871–893

    Google Scholar 

  33. Nau WM (1997) Organic tri- and tetraradicals with high-spin or low-spin states. Angew Chem Int Ed Engl 36:2445–2448

    CAS  Google Scholar 

  34. Crayston JA, Devine JN, Walton JC (2000) Conceptual and synthetic strategies for the preparation of organic magnets. Tetrahedron 56:7829–7857

    CAS  Google Scholar 

  35. Longuet-Higgins HC (1950) Molecular orbital calculations of porphine and tetrahydroporphine. J Chem Phys 18:1174–1181

    CAS  Google Scholar 

  36. Ovchinnikov AA (1978) Multiplicity of ground-state of large alternant organic molecules with conjugated bonds Theor Chim Acta 47:297–304

    CAS  Google Scholar 

  37. Tomioka H, Hirai K, Fujii C (1992) Flash-photolysis of highly hindered diarylcarbenes – optical-absorption spectrum and reaction-kinetics of 2,2’′,4,4’′,6,6’′-hexachloro-diphenylcarbene. Acta Chem Scand 46:680–682

    CAS  Google Scholar 

  38. Tomioka H, Hattori M, Hirai K (1996) Anomalous effects of para substituents on the stability of sterically congested triplet diarylcarbenes. The first triplet carbene surviving over minutes under normal conditions. J Am Chem Soc 118:8723–8724

    CAS  Google Scholar 

  39. Borden WT, Iwamura H, Berson JA (1994) Violations of Hunds rule in non-Kekulé hydrocarbons–theoretical prediction and experimental verification. Acc Chem Res 27:109–116

    CAS  Google Scholar 

  40. Borden WT, Davidson ER (1977) Effects of electron repulsion in conjugated hydrocarbon diradicals. J Am Chem Soc 99:4587–4594

    CAS  Google Scholar 

  41. Borden WT (1982) Diradicals. Wiley, New York

    Google Scholar 

  42. Dowd P, Sachdev K (1967) Trimethylenemethane from photolysis of 3-methylenecyclobutanone. J Am Chem Soc 89:715–716

    CAS  Google Scholar 

  43. Dowd P, Chang W, Paik YH (1986) Tetramethyleneethane, a ground-state triplet. J Am Chem Soc 108:7416–7417

    CAS  Google Scholar 

  44. Dowd P, Chang W, Paik YH (1987) The 2,3-dimethylenecyclohexa-1,3-diene diradical is a ground-state triplet. J Am Chem Soc 109:5284–5285

    CAS  Google Scholar 

  45. Du P, Borden WT (1987) Abinitio calculations predict a singlet ground-state for tetramethyleneethane. J Am Chem Soc 109:930–931

    CAS  Google Scholar 

  46. Prasad BLV, Rhadhakrishnan TP (1992) Dependence of spin coupling in non-Kekulé molecules on the pi-electron network. J Phys Chem 9232–9235

    Google Scholar 

  47. Nachtigall P, Jordan KD (1992) Theoretical study of the low-lying triplet and singlet-states of diradicals: tetramethyleneethane J Am Chem Soc 114:4743–4747

    CAS  Google Scholar 

  48. Pranata J (1992) Spin preferences of conjugated polyradicals – the disjoint NBMO analysis. J Am Chem Soc 114:10537–10541

    CAS  Google Scholar 

  49. Nachtigall P, Jordan KD (1993) Theoretical study of the low-lying triplet and singlet states of tetramethyleneethane – prediction of triplet below singlet-state at the triplet equilibrium geometry. J Am Chem Soc 115:270–271

    CAS  Google Scholar 

  50. Matsuda K, Iwamura H (1997) Singlet and triplet states are degenerate in 2,3-dimethylenecyclohexane-1,4-diyl. J Am Chem Soc 119:7412–7413

    CAS  Google Scholar 

  51. Matsuda K, Iwamura H (1998) Demonstration of the degeneracy of the singlet and triplet states in 2,3-dimethylenecyclohexane-1,4-diyl by measurement of its magnetic properties. J Chem Soc Perkin II 1023–1026

    Google Scholar 

  52. Platz MS, McBride JM, Little RD, Harrison JJ, Shaw A, Potter SE, Berson JA (1976) Triplet ground-states of trimethylenemethanes. J Am Chem Soc 98:5725–5726

    CAS  Google Scholar 

  53. Berson JA (1982) Capturable diradicals of the trimethylenemethane series. In: Borden WT (ed) Diradicals. Wiley

    Google Scholar 

  54. Shultz DA (1999) Conformational exchange modulation in trimethylenemethane-type biradicals. In: Lahti PM (ed) Magnetic properties of organic materials. Marcel Decker, New York

    Google Scholar 

  55. Shultz DA, Boal AK, Farmer GT (1997) The biradical, bis(3,5-di-tert-butyl-4-phenoxyl)methyleneadamantane, exhibits matrix-dependent EPR spectra suggesting rotamer bistability with differential exchange coupling. J Am Chem Soc 119: 3846–3847

    CAS  Google Scholar 

  56. Rule M, Matlin AR, Seeger DE, Hilinski EF, Dougherty DA, Berson JA (1982) Non-Kekulé molecules derived conceptually by heteroatom for carbon substitution in alternant hydrocarbons- m-quinomethane and m-naphthoquinomethane. Tetrahedron 38:787–798

    CAS  Google Scholar 

  57. Roth WR, Langer R, Bartmann M, Stevermann B, Maier G, Reisenauer HP, Sustmann R, Müller W (1987) The diradical 2,3,5,6-tetramethylene-1,4-caclohexanediyl (1,2,4,5-tetramethylenebenzene. Angew Chem Int Ed 26:256–258

    Google Scholar 

  58. Roth WR, Kowalzik U, Meier G, Reisenauer HP, Sustmann R, Müller M (1987) 2,2-Dimethyl-4,5-dimethylene-1,3-cyclopentanediyl. Angew Chem Int Ed 26:1285–1287

    Google Scholar 

  59. Reynolds JH, Berson JA, Kumashiro KK, Duchamp JC, Zilm K, Rubello A, Vogel P (1992) A kinetically stable singlet-state of 1,2,4,5-tetramethylenebenzene. J Am Chem Soc 114:763–764

    CAS  Google Scholar 

  60. Buchwalter SL, Closs GL (1979) Electron-spin resonance and CIDNP studies on 1,3-cyclopentadiyls – localized 1,3 carbon biradical system with a triplet ground-state – tunneling in carbon-carbon bond formation. J Am Chem Soc 101:4688–4694

    CAS  Google Scholar 

  61. Berson JA (1997) A new class of non-Kekulé molecules with tunable singlet-triplet energy spacings. Acc Chem Res 30:238–144

    CAS  Google Scholar 

  62. Bush LC, Heath RB, Feng XW, Wang PA, Maksimovic L, Song AI, Chung WS, Berinstain AB, Scaiano AB, Berson JA (1997) Tuning the singlet-triplet energy gap in a non-Kekule series by designed structural variation the singlet states of N-substituted-3,4-dimethylenepyrrole biradicals. J Am Chem Soc 119:1406–1415

    CAS  Google Scholar 

  63. Calder A, Forrester AR, James PG, Luckhurst GR (1969) Nitroxide radicals: V N,N’-di-t-butyl-m-phenylenebinitroxide a stable triplet. J Am Chem Soc 91:3724–3725

    CAS  Google Scholar 

  64. Dvolaitzki M, Chiarelli R, Rassat A (1992) Stable N,N’-di-t-butyl-meta-phenylene-bisnitroxides – unexpected ground state singlets. Angew Chem Int Ed Engl 31:180–181

    Google Scholar 

  65. Chiarelli R, Gambarelli S, Rassat A (1997) Exchange interactions in nitroxide biradicals. Mol Cryst Liq Cryst 305:455–478

    CAS  Google Scholar 

  66. Kanno F, Inoue K, Koga N, Iwamura H (1993) 4,6-Dimethoxy-1,3-phenylylenebis(N-tert-butyl nitroxide) with a singlet ground-state – formal violation of a rule that m-phenylene serves as a robust ferromagnetic coupling unit. J Am Chem Soc 115:847–850

    CAS  Google Scholar 

  67. Fang S, Lee MS, Hrovat DA, Borden WT (1995) Ab-initio calculations show why m-phenylene is not always a ferromagnetic coupler. J Am Chem Soc 117:6727–6731

    CAS  Google Scholar 

  68. Fujita F, Tanaka M, Suemune H, Koga N, Matsuda K, Iwamura H (1996) Antiferromagnetic exchange interaction among the three spins placed in an isosceles triangular configuration in 2,4-dimethoxy-1,3,5-benzenetriyltris(N-tert-butyl nitroxide). J Am Chem Soc 118:9347–9351

    CAS  Google Scholar 

  69. Rajca A, Lu K, Rajca S, Ross CR (1999) Singlet-triplet bistability in a 1,3-phenylene-based bis(aminoxyl) diradical. Chem Commun 1249–1250

    Google Scholar 

  70. Okada K, Imakura T, Oda M, Baumgarten M (1996) 10,10’′-(m- and p-phenylene)diphenothiazine dications: violation of a topology rule in heterocyclic high-spin pi-systems. J Am Chem Soc 118:3047–3048

    CAS  Google Scholar 

  71. Friedrich J (1997) Elektronische Eigenschaften ausgewählter konjugierter Kohlenwasserstoffe und heteroaromatischer Systeme. PhD, thesis Mainz

    Google Scholar 

  72. Veciana J, Vidal J, Jullian N (1989) Is the orthogonality of partially filled orbitals in a regular chain a proper strategy towards high-spin molecules. Mol Cryst Liq Cryst 176:443–449

    CAS  Google Scholar 

  73. Müller U, Baumgarten M (1995) Novel oligo(9,10-anthrylene)s – models for Electron-transfer and high-spin formation. J Am Chem Soc 117:5840–5850

    Google Scholar 

  74. Baumgarten M, Gherghel L, Friedrich J, Jurczok M, Rettig W (2000) Electronic decoupling in ground and excited states of asymmetric biaryls. J Phys Chem 104:1130–1140

    CAS  Google Scholar 

  75. Inoue K, Iwamura H (1995) 2-P-(N-tert-butyl-N-oxyamino)phenyl-4,4,5,5-tetramethyl-4,5-dihydroimidazol-3-oxide-1-oxyl, a stable diradical with a triplet ground-state Angew Chem Int Ed 34:927–928

    Google Scholar 

  76. Kumagai H, Hosokoshi Y, Markosyan AS, Inoue K (2001) Synthesis, structure and magnetic properties of bis(hexafluoroacetylacetonato)Mn(II) complex with a novel triplet organic radical, 4-N-tert-butylaminoxyl-4’′-nitronylnitroxylbiphenyl. Polyhedron 20:1329–1333

    CAS  Google Scholar 

  77. Karabunarliev S, Baumgarten M (1999) Reverting the effect of magnetic couplers in bridged di- and polyradicals. Chem Phys 244:35–47

    Google Scholar 

  78. Karabunarliev S, Baumgarten M (2000) Using antiferromagnetic couplers for high-spin ground states in ion radicals. Chem Phys 254239–247

    Google Scholar 

  79. Harfmann C (1996) PhD thesis. Ludwig Maximilian Univ Munich

    Google Scholar 

  80. Saunders M, Berger R, Jaffe A, McBride JM, ONeill J, Breslow R, Hoffmann JM, Perchonock C, Wassermann E, Hutton RS, Kuck VJ (1973) Unsubstituted cyclopentadienyl cation, a ground-state triplet. J Am Chem Soc 95:3017–3018

    CAS  Google Scholar 

  81. Breslow R, Hill R, Wassermann E (1964) Pentachlorocyclopentadienyl cation ground-state triplet. J Am Chem Soc 86:5349–5350

    CAS  Google Scholar 

  82. Breslow R, Chang HW, Hill R, Wassermann E (1967) Stable triplet states of some cyclopentadienyl cations. J Am Chem Soc 89:1112–1113

    CAS  Google Scholar 

  83. Wassermann E, Hutton RS, Kuck VJ, Chandross EA (1974) Dipositive ion of hexachlorobenzene- ground-state triplet. J Am Chem Soc 96:1965–1966

    Google Scholar 

  84. Breslow R, Chang HW, Yager WA (1963) A stable triplet of pentaphenylcyclopentadienyl cation. J Am Chem Soc 85:2033–2034

    CAS  Google Scholar 

  85. Broser W, Kurreck H, Siegele P (1967) Ueber substituierte pentaphenyl-cyclopentadienyl-Verbindungen und tetracyclone. 3 Symmetrische cyclopentadienyl Kationen mit nachweisbaren Triplettzuständen. Chem Ber 100:788–794

    CAS  Google Scholar 

  86. Halleux A, Martin RH, King GSD (1958) Synthese dans la serie des derives polycycliques aromatique hautement condenses- hexabenzo-1,12–2,3–4,5–6,7–8,9–10,11-coronene, le tetrabenzo-4,5–6,7–11,12–13,14-peropyrene et le tetrabenzo-1,2–3,4–8,9–10,11-bisanthene. Helv Chim Acta 41:1177–1183

    CAS  Google Scholar 

  87. Jesse RE, Biloen P, Prins R, van Voorst JDW, Hoijtink GJ (1963) Hydrocarbon ions with triplet ground states. Mol Phys 6:633–635

    CAS  Google Scholar 

  88. van Willigen H, van Broekhaven JAM, de Boer E (1967) An ESR study of mono and dinegative ions of triphenylene. Evidence for Jahn-Teller instability of triplet dianion. Mol Phys 12:533–548

    Google Scholar 

  89. Bechgaard K, Parker VD (1972) Monocations, dications, and trications of hexamethoxytriphenylene- novel anodic trimerization. J Am Chem Soc 94:4749–4750

    CAS  Google Scholar 

  90. Breslow R, Jaun B, Kluttz RQ, Xia CZ (1982) Ground-state pi-electron triplet molecules of potential use in the synthesis of organic ferromagnets. Tetrahedron 38:863–867

    CAS  Google Scholar 

  91. LePage TG, Breslow R (1987) Charge-transfer complexes as potential organic ferromagnets. J Am Chem Soc109:6412–6421

    CAS  Google Scholar 

  92. Breslow R, Maslak P, Thomaides JS (1984) Synthesis of the hexaaminobenzene derivative hexaazaoctadecahydrocoronene (HOC) and related cations. J Am Chem Soc 106:6453–6454

    CAS  Google Scholar 

  93. Breslow R (1985) Approaches to organic ferromagnets. Mol Cryst Liq Cryst 125:261–267; (1989) 4 N pi-electron triplet species and their potential use in organic ferromagnets. ibid 176:199–210

    Google Scholar 

  94. Breslow R (1999) Antiaromatic triplet ground state molecules. In Lahti PM (ed) Magnetic properties of organic materials. Marcel Decker, New York

    Google Scholar 

  95. Thomaides JS, Maslak P, Breslow R (1988) Electron-rich hexasubstituted benzene-derivatives and their oxidized cation radicals with potential triplet ground-states and polycations. J Am Chem Soc 110:3970–3979

    CAS  Google Scholar 

  96. Hoffman BM, Gamble FR, McConell HM (1967) Interactions between molecules and superconductors. J Am Chem Soc 89:27–30

    CAS  Google Scholar 

  97. Miller JS, Dixon DA, Calabrese JC (1988) Crystal-structure of hexaazaoctadecahydrocoronene dication [HAOC]2+, a singlet benzene dication. Science 240:1185–1188

    CAS  Google Scholar 

  98. Dixon DA, Calabrese JC, Harlow RL, Miller JS (1989) The structure of the tetracation of hexaazaoctadecahydrocoronene, a simple substituted benzene. Angew Chem Int Ed 28:92–94

    Google Scholar 

  99. Glasbeek M, van Voorst JDW, Hoijtink GJ (1966) Coronene dinegative ion. A thermally excitet triplet state. J Chem Phys 45:1852–1853

    CAS  Google Scholar 

  100. Krusic P J, Wassermann E (1991) Coronene dication – a thermally accessible triplet. J Am Chem Soc 113:2322–2323

    CAS  Google Scholar 

  101. Baumgarten M, Gherghel L, Wagner M, Weitz A, Rabinovitz M, Cheng PC, Scott LT (1995) Corannulene reduction – spectroscopic detection of all anionic oxidation states. J Am Chem Soc 117:6254–6257

    CAS  Google Scholar 

  102. Gherghel L, Brandt JD, Baumgarten M, Müllen K (1999) Exceptional triplet and quartet states in highly charged hexabenzocoronenes. J Am Chem Soc 121:8104–8105

    CAS  Google Scholar 

  103. Baumgarten M, Gügel A, Gherghel L (1993) EPR and optical-absorption spectra of reduced buckminsterfullerene. Adv Mater 5:458–461

    CAS  Google Scholar 

  104. Friedrich J, Baumgarten M (1997) Development and application of a new electrochemical cell allowing EPR/ENDOR and NIR measurements. Appl Magn Res 13:393–403

    CAS  Google Scholar 

  105. Shohoji MCBL, Franco MLTMB, Lazana MCRLR, Nakazawa S, Sato K, Shiomi D, Takui T (2000) Electronic quartet and triplet states of polyanionic C-60 fullerene and their anomalous spin relaxation as studied by cw-ESR/2D-Electron spin transient nutation spectroscopy. J Am Chem Soc122:2962–2963

    CAS  Google Scholar 

  106. Fässler TF, Hoffmann R, Hoffmann S, Wörle M (2000) Triple-decker type coordination of a fullerene trianion in [K([18]crown-6)](3)[eta(6),eta(6)-C-60](eta(3)-C6H5CH3)(2) - Single crystal structure and magnetic properties. Angew Chem Int Ed 39:2091–2094

    Google Scholar 

  107. Kothe G, Ohmes E, Brickmann J, Zimmermann H (1971) 1,3,5-Benzenetriyltri[di(para-biphenyl)methyl], a radical having a quartet ground state that dimerizes by entropy bonding. Angew Chem Int Ed 10:938–940

    CAS  Google Scholar 

  108. Brickmann J, Kothe G (1973) ESR of quartet states of randomly oriented molecules – calculation of line shape and detection of zero-field splitting. J Chem Phys 59:2807–2814

    CAS  Google Scholar 

  109. Rajca, A, Utamapanya, S (1993) Poly(arylmethyl) quartet triradicals and quintet tetraradicals. J Am Chem Soc 115:2396–2401 166 double!

    Google Scholar 

  110. Yoshizawa K, Chano A, Ito A, Tanaka K, Yamabe T, Fujita H, Yamauchi J, Shiro M (1992) ESR of the cationic triradical of 1,3,5-tris(diphenylamino)benzene. J Am Chem Soc 114:5994–5998

    CAS  Google Scholar 

  111. Stickley KR, Blackstock SC (1994) Triplet dication and quartet trication of a triaminobenzene. J Am Chem Soc 116:11576–11577

    CAS  Google Scholar 

  112. Dollish FR, Hall WK (1965) On interaction of triphenylamine with iodine and with silica-alumina catalysts. J Phys Chem 69:2127–2129

    CAS  Google Scholar 

  113. Wilker W, Kothe G, Zimmermann H (1975) 1,3,5-Benzenetris(diphenylmethyl)–tetramers and quartet state. Chem Berichte 108:2124–2136

    CAS  Google Scholar 

  114. Sato K, Yano M, Furuichi M, Shiomi D, Takui T, Abe K, Itoh K, Higuchi A, Katsuma K, Shirota Y (1997) Polycationic high-spin states of one- and two-dimensional (diarylamino)benzenes, prototypical model units for purely organic ferromagnetic metals as studied by pulsed ESR/electron spin transient nutation spectroscopy. J Am Chem Soc 119:6607–6613

    CAS  Google Scholar 

  115. Wienk MM, Janssen RAJ (1997) High-spin cation radicals of meta-para aniline oligomers. J Am Chem Soc 119:4492–4501

    CAS  Google Scholar 

  116. Wienk MM, Janssen RJA (1997) High-spin m-p-aniline oligo(cation radical)s. Synth Met 85:1725–1726

    CAS  Google Scholar 

  117. Struik MP (2001) High spin through bond and space. PhD thesis, Eindhoven

    Google Scholar 

  118. Selby T D, Stickley KR, Blackstock SC (2000) Triamino-s-triazine triradical trications. An experimental study of triazine as a magnetic coupling unit. Org Lett 2:171–174

    CAS  Google Scholar 

  119. Zhang J P, Baumgarten M (1997) Using triazine as coupling unit for intra and intermolecular ferromagnetic coupling. Chem Phys 214:291–299

    CAS  Google Scholar 

  120. Zhang JP, Wang RS, Wang LX, Baumgarten M (1999) Using triazine as coupling unit for intramolecular ferromagnetic coupling of multiradicals. Chem Phys 246:209–215

    CAS  Google Scholar 

  121. Nakai T, Sato K, Shiomi D, Takui T, Itoh K, Kazaki M, Okada K (1999) ESR study of high-spin nitrenes with s-triazine skeleton. Synth Met 102:2265–2266

    Google Scholar 

  122. Ishida T, Iwamura H (1991) Bis[3-tert-butyl-5-(N-oxy-tert-butylamino)phenylo] nitroxidein a quartet ground-state – a prototype for persistent high-spin poly poly[(oxyimino)-1,3-phenylenes]. J Am Chem Soc 113:4238–4241

    CAS  Google Scholar 

  123. Kanno F, Inoue K, Koga N, Iwamura H (1993) Persistent 1,3,5-benzenetriyltris(N-tert-butylnitroxide) and its analogs with quartet ground-states – intramolecular triangular exchange coupling among 3 nitroxide radical centers. J Phys Chem 97:13267–13272

    CAS  Google Scholar 

  124. Inoue K, Iwamura H (1994)Ferromagnetic and ferrimagnetic ordering in a 2-D network formed by manganese(II) and 1,3,5-tris[P(N-tert-butyl-N-oxyamino)phenyl]benzene. J Am Chem Soc 116:3173–3174

    CAS  Google Scholar 

  125. Inoue K, Iwamura H (1996) Spontaneous magnetization in a 2:3 complex formed by 3,4’′,5-tris(N-oxy-tert-butylamino)biphenyl and manganese(II) bis(hexafluoroacetyl-acetonate). Adv Mater 8:73–76

    CAS  Google Scholar 

  126. Inoue K (2001) Metal aminoxyl-based molecular magnets. Struct Bonding 100:61–91

    CAS  Google Scholar 

  127. Itoh T, Matsuda K, Iwamura H (1999) A triphenylamine derivative with three p-(N-tert-butyl-N-oxylamino)phenyl radical units and yet a doublet ground state. Angew Chem 38:1791–1793

    CAS  Google Scholar 

  128. Itoh T, Matsuda K, Iwamura H, Hori K (2000) Tris[p-(N-oxyl-N-tert-butylamino)phenyl] amine, -methyl, and -borane have doublet, triplet, and doublet ground states, respectively. J Am Chem Soc 122:2567–2576

    CAS  Google Scholar 

  129. Nakatsuji S, Anzai H (1997) Recent progress in the development of organomagnetic materials based on neutral nitroxide radicals and charge transfer complexes derived from nitroxide radicals. J Mater Chem 7:2161–2174

    CAS  Google Scholar 

  130. Shiomi D, Tamura M, Sawa H, Kato R, Kinoshita M (1993) Novel magnetic interactions in organic polyradical crystals based on nitronyl nitroxide. Synt Met 56:3279–3284

    CAS  Google Scholar 

  131. Catala L, Turek P, LeMoigne J, De Cian A, Kyritsakas N (2000) Synthesis of nitronyl- and imino-nitroxide-triradicals interconnected by phenyl ethynyl spacer. Tetrahedron Lett 41:1015–1018

    CAS  Google Scholar 

  132. Matsuchita M, Momose T, Shida T, Teki Y, Takui T, Itoh K (1990) Novel organic ions of high-spin states- ESR detection of a monoanion of meta-phenylenebis(phenylmethylene). J Am Chem Soc 112:4700–4702

    Google Scholar 

  133. Matsuchita M, Nakamura T, Momose T, Shida T, Teki Y, Takui T, Kinoshita M, Itoh K, (1992) Novel organic ions of high-spin states 2 Determination of the spin multiplicity of the ground-state and H-1-ENDOR study of the monoanion of meta-phenylenebis(phenylmethane). J Am Chem Soc 114:7470–7475

    Google Scholar 

  134. Matsuchita M, Nakamura T, Momose T, Shida T, Teki Y, Takui T, Kinoshita M, Itoh K (1993) Novel organic ions of high-spin states 3 ESR and H-1 ENDOR studies of a monocation of m-phenylenebis(phenylmethylene). Bull Chem Soc Jpn 1:1333–1342

    Google Scholar 

  135. Lahti PM, Esat B, Walton R (1998) 2-(4 ‘-nitrenophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1 H-imidazole-3-oxide-1-oxyl: Photogeneration of a quartet state organic molecule with both localized and delocalized spins. J Am Chem Soc 120:5122–5123

    CAS  Google Scholar 

  136. Lahti PM, Esat B, Liao Y, Serwinski P, Lan J, Walton R (2001) Heterospin organic molecules: nitrene-radical linkages Polyhedron 20:1647–1652

    CAS  Google Scholar 

  137. Matsuda K, Iwamura H (1996) Synthesis and EPR characterisation of [3-(N-ylooxy-tert-butylamino)-5-tert-butylphenyl]phenylcarbene with a quartet ground state. Chem Commun 1131–1132

    Google Scholar 

  138. Matsuda K, Iwamura H (1997) Syntheses and ESR characterizations of diphenylcarbenes carrying t-butyl nitroxide and nitronyl nitroxide radicals as substituents and having quartet ground states. Mol Cryst Liq Cryst 306:89–94

    CAS  Google Scholar 

  139. Tanaka M, Matsuda K, Itoh T, Iwamura H (1998) Syntheses and magnetic properties of stable organic triradicals with quartet ground states consisting of different nitroxide radicals. J Am Chem Soc 120:7168–7173

    CAS  Google Scholar 

  140. Izuoka A, Hiraishi M, Abe T, Sugawara T, Sato K, Takui T (2000) Spin alignment in singly oxidized spin-polarized diradical donor: Thianthrene bis(nitronyl nitroxide). J Am Chem Soc 122:3234–3235

    CAS  Google Scholar 

  141. Kumai R, Matsushita M, Izuoka A, Sugawara T (1994) Intramolecular exchange in a novel cross-conjugated spin system composed of pi-ion radical and nitronyl nitroxide. J Am Chem Soc 116:4523–4524

    CAS  Google Scholar 

  142. Sugawara T, Izuoka A (1997) Molecular magnetism: Present and future. Mol Cryst Liq Cryst 305 41–54

    CAS  Google Scholar 

  143. Seeger DA, Berson J A (1983) Quintet ground-state of a non-Kekulé tetraredical, 3,6-dimethyleneanthracenediyl-1,7-dioxy. J Am Chem Soc 105:5144–5146

    CAS  Google Scholar 

  144. Murata S, Iwamura H (1991) Magnetic interaction between the triplet centers in ethynylenebis(phenylnitrenes) and 1,3-butadiyne-1,4-diylbis(phenylnitrenes). J Am Chem Soc 113:5547–5556

    CAS  Google Scholar 

  145. Teki Y, Takui T, Itoh K (1987) Spin alignment in organic high-spin molecules- a Heisenberg Hamiltonian approach. Chem Phys Lett 142:181–186

    CAS  Google Scholar 

  146. Teki Y, Fujita I, Takui T, Kinoshita T, Itoh K (1994) Topoly and spin alignment in a novel organic high-spin molecule 3,4’′-bis(phenylmethylene)biphenyl, as studied by ESR and a generalized UHF Hubbard calculation. J Am Chem Soc 116:11499–11505

    CAS  Google Scholar 

  147. Murata S, Sugawara T, Iwamura H (1987) Magnetic interaction of diphenylcarbene units linked with an ethylenic double-bond. J Am Chem Soc 109:1266–1267

    CAS  Google Scholar 

  148. Matsumoto T, Ishida T, Koga N, Iwamura H (1992) Intramolecular magnetic coupling between 2-nitrene or 2-nitroxide units through 1,1-diphenylethylene chromophores – isomeric dinitrenes and dinitroxides related in connectivity to trimethylenemethane, tetramethyleneethane, and pentamethylenepropane. J Am Chem Soc 114:9952–9959

    CAS  Google Scholar 

  149. Ling C, Minato M, Lahti PM, van Willigen H, (1992) Models for intramolecular exchange in organic pi-conjugated open-shell systems – a comparison of 1,1-ethenediyl and carbonyl linked bis(arylnitrenes). J Am Chem Soc 114:9959–9969

    CAS  Google Scholar 

  150. Itoh K (1978) Electronic structures of aromatic hydrocarbons with high spin multiplicities in the electronic ground state. Pure Appl Chem 50:1251–1259

    CAS  Google Scholar 

  151. Kalgutkar KS, Lahti PM (1997) Rigid geometry bis(arylnitrenes) as definitive tests for angular dependence of zero-field splitting in high spin molecules. J Am Chem Soc 119:4771–4772

    CAS  Google Scholar 

  152. Lahti PM (1999) An integrated approach to organic-based molecular magnetic materials. In: Lahti PM (ed) Magnetic properties of organic materials. Marcel Dekker, New York

    Google Scholar 

  153. Jacobs SJ, Shultz DA, Jain R, Novak J, Dougherty DA (1993) Evaluation of potential ferromagnetic coupling units – the bis(TMM) approach to high-spin organic molecules. J Am Chem Soc 115:1744–1753

    CAS  Google Scholar 

  154. West AP, Silvermann SK, Dougherty DA (1996) Do high-spin topology rules apply to charged polyradicals? Theoretical and experimental evaluation of pyridiniums as magnetic coupling units. J Am Chem Soc 118:1452–1463

    CAS  Google Scholar 

  155. Bae JY, Yano M, Sato K, Shiomi D, Takui T, Kinoshita T, Abe K, Itoh K, Hong D (1999) Spin alignment in high-spin carbenes of heteroatomic pi-conjugation. Synth Met 103:2261–2262

    CAS  Google Scholar 

  156. Shiomi D, Ito K, Nishizawa M, Hase S, Sato K, Takui T, Itoh K (1999) Charged nitronyl nitroxide biradicals as building blocks for molecular ferrimagnetics. Mol Cryst Liq Cryst 334:99–108

    CAS  Google Scholar 

  157. Ziessel R, Ulrich G, Lawson R C, Echegoyen L (1999) Oligopyridine bis(nitronyl nitroxides): Synthesis, structures, electrochemical, magnetic and electronic properties. J Mater Chem 9:1435–1448

    CAS  Google Scholar 

  158. Chapyshev SV, Walton R, Sanborn JA, Lahti PM (2000) Quintet and septet state systems based on pyridylnitrenes: Effects of substitution on open-shell high-spin states. J Am Chem Soc 122:1580–1588

    CAS  Google Scholar 

  159. Rajca A, Utamapanya S (1993) Toward organic-synthesis of a magnetic particle- dendritic polyradicals with 15 and 31 centers for unpaired electrons. J Am Chem Soc 115:10688–10694

    CAS  Google Scholar 

  160. Rajca A, Rajca S (1995) Novel high-spin molecules- pi-conjugated polyradical polyanions – ferromagnetic spin coupling and electron localization. J Am Chem Soc 117:9172–9179

    CAS  Google Scholar 

  161. Baumgarten M (1995) Novel oligoradicals and high spin formation. Mol Cryst Liqu Cryst 272:331–338

    CAS  Google Scholar 

  162. Baumgarten M, Gherghel L, Wehrmeister T (1997) Novel high-spin states in reduced dibenzoylbenzenes. Chem Phys Lett 267:175–179

    CAS  Google Scholar 

  163. Hirota N, Weissman SI (1962) Spin-spin interaction in dimers of free radicals. Mol Phys 5:537–538

    CAS  Google Scholar 

  164. Fujita J, Matsuoka Y, Matsuo K, Tanaka M, Akita T, Koga N, Iwamura H (1997) Molecular structure and magnetic properties of N,N-bis{4-methoxy-3,5-bis(N-tert-butyl-N-oxyamino)phenyl)}aminoxyl An approach to a stable and high-spin pentaradical. Chem Commun 2393–2394

    Google Scholar 

  165. Takui, T, Itoh, K (1973) Detection of an aromatic hydrocarbon in its septet electronic ground state by electron spin resonance. Chem Phys Lett 19:120–124

    CAS  Google Scholar 

  166. Teki Y, Takui T, Itoh K, Iwamura H, Kobayashi K (1983) Design, preparation, and electron-spin-resonance detection of a ground-state nonet hydrocarbon as a model for one-dimensional organic ferromagnets. J Am Chem Soc 105:3722–3723

    CAS  Google Scholar 

  167. Fujita I, Teki Y, Takui T, Kinoshita T, Itoh K, Miko F, Sawaki Y, Iwamura H, Izuoka A, Sugawara T (1990) Design, preparation, and electron-spin-resonance detection of a ground-state undecet (S = 5) hydrocarbon. J Am Chem Soc 112:4074–4075

    CAS  Google Scholar 

  168. Adam W, van Barneveld C, Bottle SE, Engert H, Hanson G, Harrer HM, Heim C, Nau WM, Wang D (1996) EPR characterization of the quintet state for a hydrocarbon tetraradical with two localized 1,3-cyclopentanediyl biradicals linked by meta-phenylene as a ferromagnetic coupler. J Am Chem Soc 118:3974–3975

    CAS  Google Scholar 

  169. Adam W, Maas W (2000) EPR spectral determination of electronic substituent effects on the D values of hydrocarbon polyradicals (quintet and septet spin states) composed of localized 1,3-cyclopentanediyl spin-carrying units linked by 1,3-di- and 1,3,5-trimethylenebenzene ferromagnetic couplers. J Org Chem 65:7650–7655

    CAS  Google Scholar 

  170. Rajca A, Utamapanya S, Thayumanavan S (1992) Poly(arylmethyl) octet (S = 7/2) heptaradical and undecet (S = 5) decaradical. J Am Chem Soc 114:1884–1885

    CAS  Google Scholar 

  171. Nakamura N, Inoue K, Iwamura H, Fujioka T, Sawaki Y (1992) Synthesis and characterization of a branched-chain hexacarbene in a tridecet ground-state – an approach to superparamagnetc polycarbenes. J Am Chem Soc 114:1484–1485

    CAS  Google Scholar 

  172. Nakamura N, Inoue K, Iwamura H (1993) A branched-chain nonacarbene with a nonadecet ground-state- a step nearer to superparamagnetic polycarbenes. Angew Chem Int Ed 32:872–874

    Google Scholar 

  173. Matsuda K, Nakamura N, Takahashi K, Inoue K, Koga N, Iwamura H (1995) Design, synthesis, and characterization of 3 kinds of pi-cross conjugated hexacarbenes with high spin (S = 6) ground states. J Am Chem Soc 117:5550–5560

    CAS  Google Scholar 

  174. Matsuda K, Nakamura N, Inoue K, Koga N, Iwamura H (1996) Design and synthesis of a ‘'starburst’'-type nonadiazo compound and magnetic characterization of its photoproduct. Chem Eur J 2:259

    CAS  Google Scholar 

  175. Rajca A, Rajca S, Desai S (1995) Macrocyclic pi-conjugated carbopolyanions and polyradicals based upon calix[4]arene and calix[3]arene rings. J Am Chem Soc 117:806–817

    CAS  Google Scholar 

  176. Takui T, Sato K, Shiomi D, Itoh K, Kaneko T, Tsuchida E, Nishide H (1996) FT pulsed ESR/electron spin transient nutation (ESTN) spectroscopy applied to high-spin systems in solids; Direct evidence of a topologically controlled high-spin polymer as models for quasi 1D organic ferro- and superpara-magnets. Mol Cryst Liq Cryst 279:155–178

    CAS  Google Scholar 

  177. Nishide H, Miyasaka M, Tsuchida E (1998) High-spin polyphenoxyls attached to star-shaped poly(phenyleneninylene)s. J Org Chem 63:7399

    CAS  Google Scholar 

  178. Nishide H, Miyasaka M, Tsuchida E (1998) Average octet radical polymer: A stable polyphenoxyl with star-shaped pi conjugation. Angew Chem Int Ed 37:2400–2402

    Google Scholar 

  179. Nishide H, Kaneko T (1999) Pendant and π-conjugated organic polyradicals. In: Lahti PM (ed) Magnetic properties of organic materials. Marcel Decker, New York

    Google Scholar 

  180. Nishide H, Maeda T, Oyaizu K, Tsuchida E (1999) High-spin polyphenoxyl based on poly(1,4-phenyleneethynylene). J Org Chem 64:7129–7134

    CAS  Google Scholar 

  181. Miura Y (1999) Synthesis and properties of organic conjugated polyradicals. In: Lahti PM (ed) Magnetic properties of organic materials. Marcel Decker, New York

    Google Scholar 

  182. Miura Y, Issiki T, Ushitani Y, Teki Y, Itoh K (1996) Synthesis and magnetic behaviour of polyradical: poly(1,3-phenyleneethynylene) with pi-toporegulated pendant stable aminoxyl and imino N-oxide-aminoxyl radicals. J Mater Chem 6:1745–1750

    CAS  Google Scholar 

  183. Oka H, Tamura T, Miura Y, Teki Y (1999) Synthesis and magnetic behaviour of poly(1,3-phenylene)-based polyradical carrying N-tert-butylaminoxyl radicals. J Mater Chem 9:1227–1232

    CAS  Google Scholar 

  184. Rajca A, Lu K, Rajca S (1997) High-spin polyarylmethyl polyradical: fragment of a macrocyclic 2-strand based upon calix[4]arene rings. J Am Chem Soc 119:10335–10345

    CAS  Google Scholar 

  185. Rajca A, Rajca S, Wongsriratanakul J (1999) Very high-spin organic polymer: pi-conjugated hydrocarbon network with average spin of S > = 40. J Am Chem Soc 121:6308–6309

    CAS  Google Scholar 

  186. Rajca A, Wongsriratanakul J, Rajca S (2001) Magnetic ordering in an organic polymer. Science 294:1503–1505

    CAS  Google Scholar 

  187. Chiarelli R, Novak MA, Rassat A, Tholence JL (1993) A ferromagnetic transition at 1.48 K in an organic nitroxide. Nature 363:147–149

    CAS  Google Scholar 

  188. Banister AJ, Bricklebank N, Lavender I, Rawson JM, Gregory CI, Tannner BK, Clegg W, Egglewood MRJ, Palacio F (1996) Spontaneous magnetization in a sulfur-nitrogen radical at 36 K. Angew Chem Int Ed 35:2533–2535.

    CAS  Google Scholar 

  189. Allemand PM, Khemani KC, Koch A, Wudl F, Holczer K. Donovan S, Gruner G, Thompson JD (1991) Organic molecular soft ferromagnetism in a fullerene C60. Science 253:301–303.

    CAS  Google Scholar 

  190. Narymbetov B, Omerzu A, Kabanov V, Tokumoto M, Kobayashi H, Mihailovic D (2002) C60 molecular configurations leading to ferromagnetic exchange interactions in TDAE*C60 Phys Sol State 44:437–440

    Google Scholar 

  191. Caneschi A, Gatteschi D, Laugier J, Rey P, Sessoli R, Zanchini C (1988) Preparation, crystal structure and magnetic properties of an oligonuclear complex with 12 coupled spins and an S = 12 Ground State. J Am Chem Soc 110:2795–2799

    CAS  Google Scholar 

  192. Ferlay S, Mallah T, Ouahes R, Veillet P, Verdaguer M (1995) A room-temperature organometallic magnet based on Prussian blue. Nature 378:701–703

    CAS  Google Scholar 

  193. Manriquez JM, Yee GT, McLean RS, Epstein AJ,. Miller JS (1991) A room temperature molecular/organic-based magnet. Science 252:1415–1417

    CAS  Google Scholar 

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Acknowledgments

The author thanks his former PhD students, postdocs, and colleagues Prof. Anela Ivanova, Dr. Giorgio Zoppellaro, Prof. Chandrasekar Rajadurai, Prof. Ahmed Geies, and Dr. Stoyan Karabunarliev (Houston) for proof reading and the DFG and MPG for continuous financial support. He is indebted to Prof. Hiizu Iwamura for a workshop entitled Organic Structures and Properties during the first Gordon Conference in Fukuoka, Japan in 1996.

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  1. Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128, Mainz, Germany

    Martin Baumgarten

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  1. Department of Physics, Chemistry and Biology, Linköping University, Linköping, Sweden

    Anders Lund

  2. Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima, Japan

    Masaru Shiotani

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Baumgarten, M. (2012). High Spin Molecules Directed Towards Molecular Magnets. In: Lund, A., Shiotani, M. (eds) EPR of Free Radicals in Solids II. Progress in Theoretical Chemistry and Physics, vol 25. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-4887-3_5

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