Stable (long-bonded) dimers via the quantitative self-association of different cationic, anionic, and uncharged π-radicals: Structures, energetics, and optical transitions

Journal of the American Chemical Society

Volumn 125, Issue 40, 2003, Pages 12161-12171

  Lü, Jian Ming ^a   Rosokha, Sergiy V ^a   Kochi, Jay K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

SELF-ASSOCIATION REACTIONS;

ASSOCIATION REACTIONS; CHARGE TRANSFER; DIAMAGNETISM; ELECTRON TRANSITIONS; FREE RADICALS; NEGATIVE IONS; PARAMAGNETIC RESONANCE; REACTION KINETICS;

DIMERS;

2,5,8 TRIBUTYLPHENALENYL DERIVATIVE; ANION; BIPHENYL DERIVATIVE; CATION; CHLORANIL; DICHLORODICYANOQUINONE; DIMER; OCTAMETHYLBIPHENYLENE; QUINONE DERIVATIVE; RADICAL; TETRACYANOETHYLENE; TETRACYANOQUINODIMETHANE; UNCLASSIFIED DRUG;

AQUEOUS SOLUTION; ARTICLE; CHEMICAL STRUCTURE; CORRELATION ANALYSIS; COVALENT BOND; CRYSTAL STRUCTURE; DIMERIZATION; ELECTRON; ELECTRON SPIN RESONANCE; ENERGY TRANSFER; ENTHALPY; ENTROPY; INFRARED SPECTROSCOPY; MAGNETISM; MOLECULAR INTERACTION; OPTICS; QUANTITATIVE ANALYSIS; SOLID STATE; STRUCTURE ANALYSIS; THEORY; ULTRAVIOLET SPECTROSCOPY;

EID: 0141923194     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0364928     Document Type: Article

References (152)

1. (a) Ingold, K. U. In Free radicals; Kochi, J. K., Ed.; Wiley: NY, 1973; Vol. I, p 39 ff.
2. (b) Benson, S. W. Adv. Photochem. 1964, 2, 1.
3. (c) Trogler, W. C., Ed. Organometallic Radical Processes; Elsevier: NY, 1990.
4. (a) Soos, Z. G.; Klein, D. J. In Molecular Association; Foster, R., Ed.; Academic: NY, 1975; Vol. 1.
5. (b) Konno, M.; Saito, Y. Acta Clystallogr. 1974, B30, 1294.
6. (c) Miller, J. S. Ed. Extended Linear Chain Compounds; Plenum Press: NY, 1983; Vols. 2 and 3.
7. (d) Zanotti, G.; Del Pra, A.; Bozio, R. Acta Crystallogr. 1982, B38, 1225.
8. (e) Vazquez, C.; Calabrese, J. C.; Dixon, D. A.; Miller, J. S. J. Org. Chem. 1993, 58, 65.
9. (f) Johnson, M. T.; Arif, A. M.; Miller, J. S. Eur. J. Inorg. Chem. 2000, 1781.
10. (g) Novoa, J. J.; Lafuente, P.; Del Sesto, R. E.; Miller, J. S. Cryst. Eng. Comm. 2002, 4, 373.
11. (h) Awere, E. G.; Burford, N.; Haddon, R. C.; Parsons S.; Passmore, J.; Waszczak, J. V.; White, P. S. Inorg. Chem. 1990, 29, 4821.
12. (a) Gundel, D.; Sixl, H.; Metzger, R. M.; Heimer, N. E.; Harms, R. H.; Keller, H. J.; Nothe, D.; Wehe, D. J. Chem. Phys. 1983, 79, 3678.
13. (b) Grossel, M. C.; Weston S. C. Chem. Mater. 1996, 8, 977 and references therein.
14. Novoa, J. J.; Lafuente, P.; Del Sesto, R. E.; Miller, J. S. Angew. Chem., Int. Ed. 2001, 40, 2540.
15. Del Sesto, R. E.; Miller, J. S.; Lafuente, P.; Novoa, J. Chem.-Eur. J. 2002, 8, 4894.
16. Johnson, M. T.; Campana, C. F.; Foxman, B. M.; Desmarais, W.; Vela, M. J.; Miller, J. S. Chem.-Eur. J. 2000, 6, 1805.
17. (a) Miller, J. S.; Zhang, J. H.; Reiff, W. M.; Dixon, D. A.; Preston, L. D.; Reis, A. H., Jr.; Gebert, E.; Extine, M.; Troup, J.; Epstein, A.; Ward, M. D. J. Phys. Chem. 1987, 91, 4344.
18. (b) Chesnut, D. B.; Phillips, W. D. J. Chem. Phys. 1961, 35, 1002.
19. Metzger, R. M.; Heimer, N. E.; Gundel, D.; Sixl, H.; Harms, R. H.; Keller, H. J.; Nothe, D.; Wehe, D. J. Chem. Phys. 1982, 77, 6203.
20. (a) Miller, J. S.; Krusic, P. J.; Dixon, D. A.; Reiff. W. M.; Zhang, J. H.; Anderson E. C.; Epstein, A. J. J. Am. Chem. Soc. 1986, 108, 4459.
21. (b) Pasimeni, L.; Brustolon, M.; Zanonato, P. L.; Corvaja, C. Chem. Phys. 1980, 51. 381.
22. (a) Yan, Y.-K.; Mingos, M. P.; Muller, T. E.; Williams, T. E.; Kurmoo, M. J. Chem. Soc., Dalton Trans 1995, 2509.
23. (b) Marzotto, A.; Clemente, D. A.; Pasimeni, L. J. Crystallogr. Spectrosc. Res. 1988, 18. 545.
24. (a) Goto, K.; Kubo, T.; Yamamoto, K.; Nakasuji, K.; Sato, K.; Shiomi, D. ; Takui, T.; Kubota, M, Kobayashi, T.; Yakushi, K.; Ouyang, J. J. Am. Chem. Soc. 1999, 121, 1619.
25. (b) Fukui, K.; Sato, K.; Shiomi, D.; Takui, T.; Itoh, K.; Gotoh, K.; Kubo, T.; Yamamoto, K.; Nakasuji, K.; Naito, A. Synth. Met. 1999, 103, 2257.
26. (c) The four (unique) protons were unresolved within the line widths.
27. (a) Kochi, J. K.; Rathore, R.; Le Magueres, P. J. Org. Chem. 2000, 65, 6826. Note that the proton splittings of the four methyl groups at the 2, 3, 5, and 6 positions are unresolved.
28. +. was then referred to as the dimer(ic) cation radical in accord with convention. However. to avoid any further ambiguity, the latter will be consistently designated hereinafter as the pimer.
29. (c) Note that the term "pimer" was first employed by Kosower to designate what is now described herein as the "dimer"!
30. (d) See: Kosower, E. M.; Hajdu, J. J. Am. Chem. Soc. 1971, 93, 2534.
31. (a) Miller, L. L.; Mann, K. R. Acc. Chem. Res. 1996, 29, 417.
32. (b) Graf, D. D.; Duan, R. G.; Campbell, J. P.; Miller, L. L.; Mann, K. R. Am. Chem. Soc. 1997, 119, 5888.
33. (c) Penneau, J. F.; Stallman, B. J.; Kasai, P. H.; Miller, L. L. Chem. Mater. 1991, 3, 791.
34. (d) Hubig, S. M.; Kochi, J. K. J. Phys. Chem. 1995, 99, 17578.
35. (a) Hausser, K. H.; Murrell, J. N. J. Chem. Phys. 1957, 27, 500.
36. (b) Boyd, R. H.; Phillips, J. Chem. Phys. 1965, 43, 2927.
37. (c) Itoh, M. Bull. Chem. Soc. Jpn. 1972, 45, 1947.
38. (d) Chang, R. J. Phys. Chem. 1970, 74, 2029.
39. (e) Yamagishi, A. Bull. Chem. Soc. Jpn. 1975, 48, 2440.
40. (f) Bieber, A.; Andre, J. J. Chem. Phys. 1975, 7, 137.
41. (g) Nakayama S.; Suzuki, K. Bull. Chem. Soc. Jpn. 1973, 46, 3694.
42. (h) Kimura, M.; Yamada, H.; Tsubomura, H. J. Chem. Phys. 1968, 48, 440.
43. (i) Itoh. M.; Nagakura, S. J. Am. Chem. Soc. 1967, 89, 3959.
44. (j) Kosower, E. M.; Cotter, J. L. J. Am. Chem. Soc. 1964, 86, 5524.
45. (k) Sakai, N.; Shirotani, I.; Minomura, S. Bull. Chem. Soc. Jpn. 1971, 44, 675.
46. (l) Yu, Y.; Gunic, E.; Zinger, B.; Miller, L. L. J. Am. Chem. Soc. 1996, 118, 1013.
47. (m) Hill, M. G.; Mann, K. R.; Miller, L. L.; Penneau, J.-F. J. Am. Chem. Soc. 1992, 114, 2728.
48. (n) Hill, M. G.; Penneau, J. F.; Zinger, B.; Mann, K. R.; Miller, L. L. Chem. Mater. 1992, 4, 1106.
49. (o) Levillain, E.; Ronkali, J. J. Am. Chem. Soc. 1999, 121, 8760.
50. (a) Kawamori, A.; Honda, A.; Joo, N.; Suzuki, K.; Ooshika, Y. J. Chem. Phys. 1966, 44, 4363.
51. (b) Evans, A. G.; Evans. J. C.; Baker, M. W. J. Chem. Soc., Perkin Trans. 2 1975, 1310.
52. (c) Evans, A. G.; Evans, J. C.; Baker, M. W. J. Am. Chem. Soc. 1977. 99, 5882.
53. (d) Evans, A. G.; Evans, J. C.; Baker, M. W. J. Chem. Soc., Perkin Trans. 2 1977, 1787.
54. (e) Fairhurst, S. A.; Stewart, N. J.; Sutcliffe. L. H. Magn. Reson. Chem. 1987, 25, 60.
55. (f) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538.
56. (g) Grampp, G.; Landgraf, S.; Rasmussen, K.; Strauss, S. Spectrochim. Acta A 2002, 58, 1219.
57. (h) Zheng, S.; Lan, J.; Khan, S. I.; Rubin, Y. J. Am. Chem. Soc. 2003, 125, 5786.
58. (i) Gerson. F. Helv. Chim. Acta 1966, 49, 1463.
59. (j) Bowman, D. F.; Gillan, T.; Ingold, K. U. 1971, 93, 6555.
60. (k) Mendenhall, G. D.; Ingold, K. U. J. Am. Chem. Soc. 1972, 94, 7166.
61. Ganesan, V.; Rosokha, S. V.; Kochi, J. K J. Am. Chem. Soc. 2003, 125, 2559.
62. (a) Lewis, L. C.; Singer, L. S. Chem. Phys. 1965, 43, 2712.
63. (b) Howarth, O. W.; Fraenkel, G. K. J. Am. Chem. Soc. 1966, 88, 4514.
64. (c) Howarth, O. W.; Fraenkel, G. K. J. Chem. Phys. 1970, 52, 6258.
65. (d) Badger, B.; Brocklehurst, B. Nature 1968, 219, 263.
66. (e) Badger, B.; Brocklehurst, B.; Dudley, R. Chem. Phys. Lett. 1967, 1, 122.
67. (f) Badger, B.; Brocklehurst, B. Trans. Faraday Soc. 1969, 65, 2582.
68. (g) Badger, B.; Brocklehurst, B. Trans. Faraday Soc. 1969, 65, 2588.
69. (h) Badger, B.; Brocklehurst, B. Trans. Faradav Soc. 1970, 66, 2939.
70. (i) Meot-Ner, M.; Hamlet, P.; Hunter, E. P.; Field. F. H. J. Am. Chem. Soc. 1978, 100, 5466.
71. (j) Meot-Ner, M. J. Phys. Chem. 1980, 84, 2724.
72. (k) Meot-Ner, M.; El-Shall, M. S. J. Am. Chem. Soc. 1986, 108, 4386.
73. For the spectral and structural characterization of such cation-radical "pimers", see: (l) Le Magueres, P.; Lindeman, S.; Kochi, J. K. J. Chem. Soc., Perkin Trans 2 2001, 1180.
74. (m) Kochi, J. K.; Rathore, R.; Le Magueres, P. in ref 12a and references therein.
75. (n) Extensive electron delocalizations in the π-bonded pimers are indicated in the EPR spectra by twice the number of hyperfine lines with half the splittings observed in the monomeric radical.
76. +. which are one-electron pimers.
77. (p) Compare also Dewar's putative structure pertinent to the benzidene and related rearrangement. See, e.g., Miller, B. Advanced Organic Chemistry, 2nd ed.; Pearson/Prentice Hall, New York, 2003; p 119.
78. (a) Goldstein, P.; Seff, K.; Trueblood, K. N. Acta Crystallogr. 1968, B24, 778.
79. (b) Hanson, A. W. Acta Crystallogr. 1968, B24, 773.
80. (c) Kobayashi, H. Bull. Chem. Soc. Jpn. 1974, 47,1346.
81. (c) Fourmigue, M.; Perrocheau, V.; Clerac, R.; Coulon, C. J. Mater. Chem. 1997, 7, 2235.
82. (d) Ballester, L.; Gutierrez, A.; Perpinan, M. F.; Rico, S.; Azcondo, M. T.; Bellito, C. Inorg. Chem. 1999, 38, 4430.
83. (a) For the counterion effect in methyltetrahydrofuran, see Itoh in ref 14c.
84. (b) Since solubility limitations of these crystalline salts precluded the use of organic solvents of low polarity, we were unable to provide a more stringent test of the counterion effects (especially tetraalkylammonium versus alkali metal) on ion-pairing equilibria beyond that provided by acetone of moderate polarity. Nonetheless, the extensive solvent effects in Table 4 are sufficient to establish the important point that generalized ion-pairing effects do not materially affect the spectral properties of the dimer (columns 4 and 5) to the large degree that they affect the thermodynamic parameters (columns 6, 7, and 8).
85. D = 2.87 Å.
86. (b) Del Sesto. R. E.; Botoshansky, M.; Kaftory, M.; Miller. J. S. Cryst. Eng. Comm. 2002, 4, 106.
87. -. are 1.429, 1.405, and 1.170 Å and 117.7° with θ = 0°.
88. -..
89. (b) Zheludev. A.; Grand, A.; Ressouche, E.; Schwiizer, J.; Morin, B. G.; Epstein, A. J.; Dixon, D. A.; Miller, J. S. J. Am. Chem. Soc. 1994, 116, 7243.
90. 2- are (Cl)C-C(Cl) 1.364 Å, (Cl)C-C(O) 1.454 Å, C-O 1.251 Å, and C-Cl 1.726 Å.
91. (a) Iida, Y. Bull. Chem. Soc. Jpn. 1969, 42, 637.
92. (b) Oohashi, Y.; Sakata, T. Bull. Chem. Soc. Jpn. 1973, 46, 3330.
93. For example, see: (a) Hove, M. J.; Hoffman B. M.; Ibers, J. A. J. Chem. Phys. 1971, 56, 3490.
94. (b) Guirauden, A.; Johannsen. I.; Batail, P.; Coulon, C. Inorg. Chem. 1993, 32, 2446.
95. (c) Yakushi, K.; Nishimura, S.; Sugano, T.; Kuroda, H. Acta Crystallogr. 1980, B36, 358.
96. (d) Attanasio, D.; Bellitto, C.; Bonamico, M.; Fares, V.; Imperatori, P. Gazz. Chim. Ital. 1991, 121, 155.
97. (e) Forward, J. M.; Mingos, D. M. P.; Muller, T. E.; Williams, D. J.; Yan, Y.-K. J. Organomet. Chem. 1994, 467, 207.
98. (a) Sebastiano, R.; Korp, J. D.; Kochi, J. K. J. Chem. Soc. Chem. Commun. 1991, 1481.
99. (b) Bockman, T. M.; Kochi, J. K. J. Org. Chem. 1990, 55, 4127.
100. (c) Hilgers, F.; Kaim, W.; Schulz, A.; Zalis, S. J. Chem. Soc., Perkin Trans 2 1994, 135.
101. (d) Song, H.; Reed. C. A.; Scheidt. W. R. J. Am. Chem. Soc. 1989, 111, 6867.
102. (e) Nagashima, H.; Hashimoto, N.; Inoue, H.; Yoshioka, N. New J. Chem. 2003, 27, 805.
103. (a) In charge-transfer crystals, packing of the donor (D) and acceptor (A) units can occur in either two separate DDD and AAA stacks (homosoric) or single alternating DADA stacks (heterosoric).
104. D is not strongly different from that between dimer units. The counterion is most often located by the sides of the stack. By contrast, only those crystals containing discrete dimeric units and separated from neighboring dimers by intervening counterions are included in Table 5.
105. (c) For the recent classification of radical compounds according to crystal structure, see: Dahm, D. J.; Horn, P.; Johnson, G. R.; Miles, M. G.; Wilson, J. D. J. Cryst. Mol. Struct. 1975, 5, 27.
106. (a) Mulliken, R. S. J. Am. Chem. Soc. 1952, 74, 811.
107. (b) Mulliken, R. S. J. Phys. Chem. 1952, 56, 801. For the equivalent molecular-orbital formulation, see:
108. (c) Flurry, R. L. J. Phys. Chem. 1965, 69, 1927.
109. (d) Flurry, R. L. J. Phys. Chem. 1969, 73, 2111.
110. (e) Flurry, R. L. J. Phys. Chem. 1969, 73, 2787.
111. (f) Since the charge-transfer formulation has generally been applied to wholly diamagnetic systems, dimer formation as in eqs 1 and 2 can be alternatively considered from an equivalent point of view that starts from a pair of closed-shell species such as a dication and its neutral donor or a dianion and its neutral acceptor, which are more traditional charge-transfer dyads. Indeed, such an analogy has been realized in the methyl viologen systems.
112. L relationship is based on neglect of direct overlap of the π-orbitals, and we thus intend its use here to be only qualitative in nature. A more quantitative treatment of this subject will be presented in a forthcoming paper (Sun, D. L.; Rosokha, S. V.; Lindeman, S. V.; Kochi, J. K. Submitted for publication).
113. CT) with the donor/acceptor redox of or ionization potentials.
114. L in π-bonded dimers are comparable to those in related charge-transfer complexes despite the absence of a contribution from the energy difference (Δ = 0).
115. -1 in charge-transfer complexes.
116. (d) Briegleb, G. Electronen-Donator-Acceptor Komplexe; Springer: Berlin, 1961.
117. (e) Foster, R., Ed. Organic Charge-Transfer Complexes: Academic: NY, 1969.
118. (f) Foster, R., Ed. Molecular Complexes; Crane, Russak: NY, 1973.
119. (g) Creutz, C.; Newton, M. D.; Sutin, N. J. Photochem. Photobiol. A: Chem. 1994, 82, 47.
120. H is more difficult to assign with certainty. (a) We suggest that it derives from a charge-transfer transition from the subjacent HOMO-1 (of the dimer) to the LUMO (see Figure S7).
121. L cited in column 6.
122. M in the monomer indicate that the HOMO/LUMO splitting is larger than the HOMO-2/HOMO-1 splitting.
123. L in Table 1 was obtained in water.
124. (a) EPR studies of singlet → triplet transitions of the dimeric forms in solution will be reported separately.
125. -. salts in the crystalline solid state, see:(b) Flandrois, S.; Amiell. J.; Carmona, F.; Delhaes, P. Solid State Comm. 1975, 17, 287.
126. (c) Gordon, D.; Hove, M. J. J. Chem. Phys. 1973, 59, 3419.
127. 2- indicate that within 3% the interplanar separation of do = 2.90 ± 0.08 Å is quite independent of marked variations in the calculated electrostatics; see Table S4.
128. See: Table S3 in Supporting Information for details.
129. -1.
130. -1).
131. (a) Hush, N. S. Z. Elektrochem. 1957, 61, 734.
132. (b) Hush, N. S. Trans. Faraday Soc. 1961, 57, 557.
133. (c) Hush, N. S. Prog. Inorg. Chem. 1967, 8, 391.
134. (d) Hush, N. S. Electrochim. Acta. 1968, 13, 005.
135. (e) Creutz, C.; Newton, M. D.; Sutin, N. J. Photochem. Photobiol. A: Chem. 1994, 82, 47.
136. 2- are symptomatic of an attractive interaction of the carbonyl acceptor with the π-donor property of the juxtaposed (C-C) double bond.
137. (a) The dimeric nature of the ground state in Chart 4 (right) is open to question. Although it is speculatively presented here as a single (HOMO) orbital containing two electrons, a reviewer has suggested a pair of interacting SOMOs with correlated electron spins, that is, a singlet diradical.
138. (b) An ongoing collaborative program with M. Head-Gordon, Berkeley is aimed at the theoretical quantum mechanical basis for mapping out precise potential-energy surfaces and π-bonding characteristics of the two-electron dimers, with particular regard to their one-electron pimer counterparts.
139. (c) More extensive comparisons with dimer structures are not possible at this juncture owing to the paucity of precise pimer structures arising from inherently weaker one-electron bindings.
140. See: Mulliken, R. S.; Person, W. B. Molecular Complexes. Wiley: NY, 1969; p 40, Table 4-1.
141. Rathore, R.; Lindeman, S. V.; Kochi, J. K. J. Am. Chem. Soc. 1997, 119, 9393.
142. (a) In the latter context, π-dimerization can equally well result from the πr-associations of various combinations of diamagnetic cation/anion dyads.
143. . as electron acceptors) with arene donors. For example, see: Raner, K. D.; Lusztyk, J.; Ingold, K. U. J. Phys. Chem. 1989, 93, 564 and references therein.
144. D for the dimeric structure despite large differences in the homosoric/heterosoric stackings of the radical units is further indication of its structural integrity.
145. The direct relationship between the charge-transfer transition in solution and in the crystalline solid state is illustrated in Figure 6. Note that the slight red-shift in the solid-state spectra has been previously noted. See: Oohashi et al. in ref 24b, Itoh in ref 14c. Sakai et al. in ref 14k, and Miller et al. in ref 5.
146. For example, compare: Rosokha, S. V.; Kochi, J. K. J. Am. Chem. Soc. 2001. 123, 8985.
147. For example, see: (a) Farges, J.-P., Ed. Organic Conductors: Fundamentals and Applications; Marcel Dekker: NY, 1994.
148. (b) Lahti, P. M., Ed.; Magnetic Properties of Organic Materials; Marcel Dekker: NY, 1999.
149. (c) Miller, J. S., Drillon, M., Eds. Magnetism: Molecules to Materials; Wiley-VCH: Weinheim, 2001.
150. Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60. 4399.
151. Perrin, D. D.; Armagero, W. L.; Perrin, D. R. Purification of Laboratory Chemicals, 2nd ed.; Pergamon: NY, 1980.
152. Sheldrick, G. M. SHELXS-86, Program for Structure Solution; University of Gottingen: Germany, 1986.