EPR spectroscopic and computational characterization of the 2-dehydro-m-xylylene and 4-dehydro-m-xylylene triradicals

Journal of Physical Organic Chemistry

Volumn 24, Issue 10, 2011, Pages 976-992

  Neuhaus, Patrik ^a   Winkler, Michael ^a   Sander, Wolfram ^a  

^a RUHR UNIVERSITY BOCHUM   (Germany)

Author keywords

diradical; electron paramagnetic resonance spectroscopy; electronic structure theory; matrix isolation; triradical

Indexed keywords

DIRADICALS; ELECTRON PARAMAGNETIC RESONANCE SPECTROSCOPY; ELECTRONIC STRUCTURE THEORY; MATRIX ISOLATION; TRIRADICAL;

ELECTRON RESONANCE; ELECTRONIC STRUCTURE; PARAMAGNETIC MATERIALS; PARAMAGNETIC RESONANCE; PARAMAGNETISM; SPECTROSCOPY;

ELECTRON SPIN RESONANCE SPECTROSCOPY;

EID: 80053340444     PISSN: 08943230     EISSN: 10991395     Source Type: Journal    
DOI: 10.1002/poc.1911     Document Type: Conference Paper

References (140)

1. See, for example:, D. A. Dougherty, Acc. Chem. Res. 1991, 24, 88.
2. A. Rajca, Chem. Rev. 1994, 94, 871.
3. P. M. Lahti, Magnetic Properties of Organic Materials, Marcel Dekker, New York, 1999.
4. H. Iwamura, K. Inoue, T. Haymizu, Pure Appl. Chem. 1996, 68, 243.
5. K. Sato, D. Shiomi, T. Takui, M. Hattori, K. Hirai, H. Tomioka, Mol. Cryst. Liq. Cryst. 2002, 376, 549.
6. F. Hund, Z. Phys. 1928, 51, 759.
7. W. Kutzelnigg, J. D. Morgan III, Z. Phys. D 1996, 36, 197.
8. For an in-depth analysis of why Hund's rule is operative in molecules, see:, J. Katriel, R. Pauncz, Adv. Quant. Chem. 1977, 10, 143.
9. H. C. Longuet-Higgins, J. Chem. Phys. 1950, 18, 265.
10. J. E. Berson, in: Reactive Intermediate Chemistry (Eds:, R. A. Moss, M. S. Platz, M. Jones Jr.,), Wiley, Hoboken, 2004, 165.
11. V. Bonacic-Koutecky, J. Koutecky, J. Michl, Angew. Chem. Int. Ed. 1987, 26, 170.
12. H. Kollmar, V. Staemmler, Theor. Chim. Acta 1978, 48, 223.
13. W. T. Borden, H. Iwamura, J. E. Berson, Acc. Chem. Res. 1994, 27, 109.
14. W. T. Borden, E. R. Davidson, J. Am. Chem. Soc. 1977, 99, 4587.
15. For an outline of the historical development of this and related concepts, see:, W. T. Borden, J. Org. Chem. 2011, 76, 2943.
16. H. Kollmar, V. Staemmler, J. Am. Chem. Soc. 1977, 99, 3583.
17. M. J. Lenington, P. G. Wenthold, J. Phys. Chem. A 2010, 114, 1334.
18. M. L. Kearley, A. S. Ichimura, P. M. Lahti, J. Am. Chem. Soc. 1995, 117, 5235.
19. A. A. Ovchinnikov, Theor. Chim. Acta 1978, 47, 297.
20. See also:, W. T. Borden, Diradicals, Wiley-Interscience, New York, 1978.
21. H. M. McConnell, J. Chem. Phys. 1963, 39, 1910.
22. H. Iwamura, Adv. Phys. Org. Chem. 1991, 26, 179.
23. C. Kollmar, O. Kahn, Acc. Chem. Res. 1993, 26, 259.
24. P. R. Serwinski, B. Esat, P. M. Lahti, Y. Liao, R. Walton, J. Lan, J. Org. Chem. 2004, 69, 5247.
25. P. Taylor, P. R. Serwinski, P. M. Lahti, Org. Lett. 2005, 7, 3693.
26. T. L. Allen, P. M. Lahti, J. Phys. Chem. A 2011, 115, 4922.
27. See also:, L. Catala, J. DeMoigne, N. Gruber, J. J. Novoa, P. Rabu, E. Belorizky, P. Turek, Chem. Eur. J. 2005, 11, 2440.
28. Selected recent reviews on di- and tridehydrobenzenes with a focus on electronic structure, state-energy splittings, and spectroscopic characterization:, H. H. Wenk, M. Winkler, W. Sander, Angew. Chem. Int. Ed. 2003, 42, 502.
29. A. I. Krylov, J. Phys. Chem. A 2005, 109, 10638.
30. P. G. Wenthold, Aust. J. Chem. 2010, 63, 1091.
31. M. Winkler, W. Sander, Aust. J. Chem. 2010, 63, 1013.
32. For detailed discussions of the electronic structure of tridehydrobenzenes, see:, A. M. C. Cristian, Y. Shao, A. I. Krylov, J. Phys. Chem. A 2004, 108, 6581.
33. L. Koziol, M. Winkler, K. N. Houk, S. Venkataramani, W. Sander, A. I. Krylov, J. Phys. Chem. A 2007, 111, 5071.
34. S. Chattopadhyay, R. K. Chaudhuri, K. F. Freed, J. Phys. Chem. A 2011, 115, 3665.
35. For example:, R. R. Squires, C. J. Cramer, J. Phys. Chem. A 1998, 102, 9072.
36. C. J. Cramer, J. Thompson, J. Phys. Chem. A 2001, 105, 2091.
37. I. Garcia-Cruz, J. M. Martinez-Magadan, J. M. Bofill, F. Illas, J. Phys. Chem. A 2004, 108, 5111.
38. J. J. Nash, H. I. Kenttämaa, C. J. Cramer, J. Phys. Chem. A 2005, 109, 10348.
39. In some cases, e.g., 1,8-didehydronaphthalene, Ref., or in the topologically similar 1,3-didehydrofulvene, vanishing singlet-triplet gaps are found computationally, despite the close proximity of the radical sites:, M. Winkler, J. Phys. Chem. A 2005, 109, 1240.
40. B. B. Wright, M. S. Platz, J. Am. Chem. Soc. 1983, 105, 628.
41. K. Haider, M. S. Platz, A. Despres, V. Lejeune, E. Migirdicyan, T. Bally, E. Haselbach, J. Am. Chem. Soc. 1988, 110, 2318.
42. P. G. Wenthold, J. B. Kim, W. C. Lineberger, J. Am. Chem. Soc. 1997, 119, 1354.
43. T. Wang, A. I. Krylov, J. Chem. Phys. 2005, 123, 104304.
44. P. Neuhaus, D. Grote, W. Sander, J. Am. Chem. Soc. 2008, 130, 2993.
45. For a computational treatment of 1 with a focus on magnetic properties, see also:, Z. Havlas, J. Michl, J. Chem. Soc., Perkin Trans. 2, 1999, 2299, and Ref.
46. C. R. Kemnitz, R. R. Squires, W. T. Borden, J. Am. Chem. Soc. 1997, 119, 6564.
47. L. A. Hammad, P. G. Wenthold, J. Am. Chem. Soc. 2001, 123, 12311.
48. H. M. T. Nguyen, A. Dutta, K. Morokuma, M. T. Nguyen, J. Chem. Phys. 2005, 122, 154308.
49. P. Neuhaus, W. Sander, Angew. Chem. Int. Ed. 2010, 49, 7277.
50. P. G. Wenthold, S. G. Wierschke, J. J. Nash, R. R. Squires, J. Am. Chem. Soc. 1994, 116, 7378.
51. J. Cabrero, N. Ben-Amor, R. Caballol, J. Phys. Chem. A 1999, 103, 6220.
52. P. Neuhaus, S. Henkel, W. Sander, Aust. J. Chem. 2010, 63, 1634.
53. For early EPR investigations of substituted derivatives of 7 in organic glasses, see:, G. L. Closs, L. R. Kaplan, V. I. Bendall, J. Am. Chem. Soc. 1967, 89, 3376.
54. From the photoelectron spectrum of 8, a singlet-triplet energy splitting of less than 5kcal/mol has been derived:, C. F. Logan, J. C. Ma, P. Chen, J. Am. Chem. Soc. 1994, 116, 2137.
55. A matrix-isolated derivative of 8 could be investigated by IR spectroscopy and was found to have a singlet ground state:, W. Sander, H. Wandel, G. Bucher, J. Gräfenstein, E. Kraka, D. Cremer, J. Am. Chem. Soc. 1998, 120, 8480.
56. For recent reviews, see:, M. Kar, A. Basak, Chem. Rev. 2007, 107, 2861.
57. I. Alabugin, B. Breiner, M. Manoharan, Adv. Phys. Org. Chem. 2008, 42, 1.
58. A. Polukhtine, G. Karpov, D. R. Pandithavidana, A. Kuzmin, V. V. Popik, Aust. J. Chem. 2010, 63, 1099, and references given therein.
59. H. H. Wenk, W. Sander, Angew. Chem. Int. Ed. 2002, 41, 2742.
60. H. F. Bettinger, W. Sander, J. Am. Chem. Soc. 2003, 125, 9726.
61. W. Sander, M. Winkler, B. Cakir, D. Grote, H. F. Bettinger, J. Org. Chem. 2007, 72, 715.
62. W. Sander, D. Grote, S. Kossmann, F. Neese, J. Am. Chem. Soc. 2008, 130, 4396.
63. D. Grote, C. Finke, S. Kossmann, F. Neese, W. Sander, Chem. Eur. J. 2010, 16, 4496.
64. M. Winkler, J. Phys. Chem. A 2008, 112, 8649.
65. N. R. Wijerantne, M. Da Fonte, A. Ronenius, P. J. Wyss, D. Tahmassebi, P. G. Wenthold, J. Phys. Chem. A 2009, 113, 9467.
66. L. V. Slipchenko, T. E. Munsch, P. G. Wenthold, A. I. Krylov, Angew. Chem. Int. Ed. 2004, 43, 742.
67. H. M. T. Nguyen, G. Gopakumar, J. Peeters, M. T. Nguyen, J. Phys. Chem. A 2004, 108, 8411.
68. H. M. T. Nguyen, G. Gopakumar, J. Peeters, M. T. Nguyen, J. Phys. Chem. A 2005, 109, 720.
69. T. Wang, A. I. Krylov, Chem. Phys. Lett. 2006, 425, 196.
70. For a detailed study of the 5-dehydro-m-xylylene anion, see:, T. E. Munsch, L. V. Slipchenko, A. I. Krylov, P. G. Wenthold, J. Org. Chem. 2004, 69, 5735.
71. The bis-(bromomethyl)iodobenzenes were prepared by bromination of the corresponding dimethyliodobenzenes. For detailed procedures, see:, P. Neuhaus, Ph.D. Thesis, Ruhr-Universität Bochum, 2010 ().
72. M. Griffin, A. Muys, C. Noble, D. Wang, C. Eldershaw, K. E. Gates, K. Burrage, G. R. Hanson, Mol. Phys. Rep. 1999, 26, 60.
73. C. Hampel, K. Peterson, H.-J. Werner, Chem. Phys. Lett. 1992, 190, 1.
74. P. J. Knowles, C. Hampel, H.-J. Werner, J. Chem. Phys. 1993, 99, 5219.
75. P. J. Knowles, C. Hampel, H.-J. Werner, J. Chem. Phys. 2000, 112, 3106.
76. B. O. Roos, P. R. Taylor, P. E. M. Siegbahn, Chem. Phys. 1980, 48, 157.
77. P. Celani, H.-J. Werner, J. Chem. Phys. 2000, 112, 5546.
78. H.-J. Werner, Mol. Phys. 1996, 89, 645.
79. H.-J. Werner, Adv. Chem. Phys. 1987, 59, 1.
80. H.-J. Werner, P. J. Knowles, J. Chem. Phys. 1988, 89, 5803.
81. H.-J. Werner, P. J. Knowles, Chem. Phys. Lett. 1988, 145, 514.
82. S. R. Langhoff, E. R. Davidson, Int. J. Quantum Chem. 1974, 8, 61.
83. W. Duch, G. H. F. Diercksen, J. Chem. Phys. 1994, 101, 3018.
84. For the Davidson correction, relaxed reference energies were employed throughout, c.f., H.-J. Werner, M. Kallay, J. Gauss, J. Chem. Phys. 2008, 128, 03430.
85. R. J. Gdanitz, R. Ahlrichs, Chem. Phys. Lett. 1988, 143, 413.
86. P. G. Szalay, R. J. Bartlett, J. Phys. Chem. 1995, 103, 3600.
87. T. H. Dunning Jr., J. Chem. Phys. 1989, 90, 1007.
88. H.-J. Werner, P. J. Knowles, Molpro 2009.1; Birmingham, 2008.
89. W. J. Hehre, R. Ditchfield, J. A. Pople, J. Chem. Phys. 1972, 56, 2257.
90. A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
91. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and, D. J. Fox, Gaussian09, Gaussian, Inc., Wallingford CT, 2009.
92. R. S. Mulliken, J. Chem. Phys. 1955, 23, 1833, 1841, 2338, 2343.
93. T. A. Keith, AIMALL, Version 11.04.03, 2011.
94. T. Lu, Multiwfn, Version 2.01, Beijing, 2011.
95. F. Neese, ORCA-An Ab Initio, DFT and Semiempirical electronic structure package, 2.7. University of Bonn, 2009.
96. V. Barone, in: Recent Advances in Density Functional Methods, Part I (Ed:, D. P. Chong,), World Scientific, Singapore, 1996.
97. S. Stoll, A. Schweiger, J. Magn. Reson. 2006, 178, 42.
98. R. Marquardt, A. Balster, W. Sander, E. Kraka, D. Cremer, J. G. Radziszewski, Angew. Chem. Int. Ed. 1998, 37, 955.
99. H. H. Wenk, W. Sander, Chem. Eur. J. 2001, 7, 1837.
100. H. H. Wenk, W. Sander, Eur. J. Org. Chem. 2002, 3927.
101. W. Sander, M. Exner, M. Winkler, A. Balster, A. Hjerpe, E. Kraka, D. Cremer, J. Am. Chem. Soc. 2002, 124, 13072.
102. M. Winkler, B. Cakir, W. Sander, J. Am. Chem. Soc. 2004, 126, 6135.
103. S. Venkataramani, M. Winkler, W. Sander, Angew. Chem. Int. Ed. 2005, 44, 6306.
104. S. Venkataramani, M. Winkler, W. Sander, Angew. Chem. Int. Ed. 2007, 46, 4888.
105. B. J. Jankiewicz, J. N. Reece, N. R. Vinueza, J. J. Nash, H. I. Kenttämaa, Angew. Chem. Int. Ed. 2008, 47, 9860.
106. H. A. Lardin, J. J. Nash, P. G. Wenthold, J. Am. Chem. Soc. 2002, 124, 12612.
107. J. A. Berson, in: The Chemistry of Quinonoid Compounds (Eds:, S. Patai, Z. Rappaport,), Wiley, New York, 1988, Vol. II; 462.
108. A. M. Trozollo, E. Wasserman, in: Carbenes (Eds:, R. A. Moss, M. Jones Jr.,), Wiley-Interscience, New York, 1976, Vol. II, Chapter 5.
109. R. S. Hutton, H. D. Roth, J. Am. Chem. Soc. 1982, 104, 7395.
110. W. Adam, F. Kita, H. M. Harrer, W. M. Nau, R. Zipf, J. Org. Chem. 1996, 61, 7056.
111. W. Adam, H. M. Harrer, T. Heidenfelder, T. Kammel, F. Kita, W. M. Nau, C. Sahin, J. Chem. Soc., Perkin Trans. 1996, 2, 2085.
112. W. Adam, F. Kita, H. M. Harrer, W. M. Nau, Pure Appl. Chem. 1997, 69, 91.
113. W. Adam, H. M. Harrer, F. Kita, W. M. Nau, Adv. Photochem. 1998, 24, 205.
114. W. Adam, O. Emmert, T. Heidenfelder, J. Org. Chem. 1999, 64, 3417.
115. W. Adam, C. M. O. Schulte, J. Org. Chem. 2002, 67, 4569.
116. S. Sinnecker, F. Neese, J. Phys. Chem. A 2006, 110, 12267, and references given therein.
117. D. Ganyushin, F. Neese, J. Chem. Phys. 2006, 125, 024103.
118. J. E. Harriman, Theoretical Foundations of Electron Spin Resonance, Academic Press, London, 1978.
119. See also:, O. Vahtras, O. Loboda, B. Minaev, H. Agren, K. Ruud, Chem. Phys. 2002, 279, 133.
120. H. M. McConnell, J. Chem. Phys. 1958, 28, 1188.
121. H. M. McConnell, J. Strathdee, Mol. Phys. 1959, 2, 129.
122. P. H. Kasai, J. Am. Chem. Soc. 1972, 94, 5950.
123. E. R. Davidson, J. Chem. Phys. 1967, 46, 3320.
124. A. E. Clark, E. R. Davidson, J. Chem. Phys. 2001, 115, 7382.
125. E. R. Davidson, A. E. Clark, Mol. Phys. 2002, 100, 373.
126. A. E. Clark, E. R. Davidson, J. Phys. Chem. A 2002, 106, 6890.
127. A. E. Clark, E. R. Davidson, Int. J. Quant. Chem. 2003, 93, 384.
128. C. Herrmann, M. Reiher, B. A. Hess, J. Chem. Phys. 2005, 122, 034102.
129. M. Reiher, Faraday Discuss. 2007, 135, 97, and references given therein.
130. R. W. F. Bader, Atoms in Molecules: A Quantum Theory, Oxford University Press, New York, 1994.
131. For example:, C. Remenyi, R. Reviakine, M. Kaupp, J. Phys. Chem. B 2007, 111, 8290.
132. A. Carrington, I. C. P. Smith, Mol. Phys. 1965, 9, 138.
133. R. McWeeny, Y. Mizuno, Proc. R. Soc. London 1961, 259, 554.
134. A. Rajca, A. Olankitwanit, S. Rajca, J. Am. Chem. Soc. 2011, 133, 4750.
135. See also:, A. Rajca, K. Shiraishi, S. Rajca, Chem. Commun. 2009, 4372.
136. A. Rajca, M. Takahashi, M. Pink, G. Spagnol, S. Rajca, J. Am. Chem. Soc. 2007, 129, 10159.
137. R. J. Fehir, Jr., J. K. McCusker, J. Phys. Chem. A 2009, 113, 9249.
138. For example:, S. A. Wolf, D. D. Awshalom, R. A. Buhrmann, J. M. Daughton, S. von Molnar, M. L. Roukes, A. Y. Chtchelkanova, D. M. Treger, Science 2001, 294, 1488.
139. A. Fert, Rev. Mod. Phys. 2008, 80, 1517.
140. L. Bogani, W. Wernsdorfer, Nat. Mater. 2008, 7, 179.