Spectroscopic demonstration of a large antisymmetric exchange contribution to the spin-frustrated ground state of a D3 symmetric hydroxy-bridged trinuclear Cu(II) complex: Ground-to-excited state superexchange pathways

Journal of the American Chemical Society

Volumn 126, Issue 39, 2004, Pages 12586-12595

  Yoon, Jungjoo ^a   Mirica, Liviu M ^a   Stack, T Daniel P ^a   Solomon, Edward I ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTIFERROMAGNETISM; CHEMICAL BONDS; COMPLEXATION; GROUND STATE; HAMILTONIANS; HYDROXYLATION; PARAMAGNETIC RESONANCE; PARAMETER ESTIMATION; SINGLE CRYSTALS;

MAGNETIC CIRCULAR DICHROISM (MCD); TRIMERS; TRINUCLEAR COMPLEXES; VARIABLE-TEMPERATURE VARIABLE-FIELD MCD (VTVH MCD);

COPPER;

COPPER COMPLEX;

ANTIFERROMAGNETISM; ANTISYMMETRIC EXCHANGE; ARTICLE; CHEMICAL BOND; CIRCULAR DICHROISM; ELECTRON; ELECTRON SPIN RESONANCE; EXCITATION; GROUND TO EXCITED STATE SUPEREXCHANGE PATHWAY; JAHN TELLER EFFECT; MAGNETIC FIELD; MAGNETISM; PARAMETER; POWDER SINGLE CRYSTAL ELECTRIN SPIN RESONANCE; QUANTUM CHEMISTRY; SIGMA BOND; SPECTROSCOPY; SPIN FRUSTRATED GROUND STATE; SPIN HAMILTONIAN PARAMETER; SYMMETRY LOWERING; TEMPERATURE; VARIABLE TEMPERATURE VARIABLE MAGNETIC FIELD CIRCULAR DICHROISM;

CATIONS, DIVALENT; CIRCULAR DICHROISM; COPPER; EDETIC ACID; ELECTRON SPIN RESONANCE SPECTROSCOPY; MODELS, CHEMICAL; ORGANOMETALLIC COMPOUNDS;

EID: 4644311323     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja046380w     Document Type: Article

References (102)

1. See the thematic (Biomimetic Inorganic Chemistry) issue of Chem. Rev. 2004, 104 (2), 347-1200.
2. (a) Holm, R. H.; Kennepohl, P.; Solomon, E. I. Chem. Rev. 1996, 96, 2239-2314.
3. (b) Beinert, H.; Holm, R. H.; Münck, E. Science 1997, 277, 653-659.
4. (a) Miller, J. S.; Drillon, M. Magnetism: Molecules to Materials; Wiley-VCH: Weinheim, 2001; Vols. 1-4.
5. (b) Kahn, O. Molecular Magnetism; VCH: New York, 1993.
6. (a) Beckett, R.; Colton, R.; Hoskins, B. F.; Martin, R. L.; Vince, D. G. Aust. J. Chem. 1969, 22, 2527-2533.
7. (b) Beckett, R.; Hoskins, B. F. J. Chem. Soc., Dalton Trans. 1972, 291-295.
8. (c) Ross, P. F.; Murmann, R. K.; Schlemper, E. O. Acta Crystallogr. 1974, B30, 1120-1123.
9. (d) Butcher, R. J.; O'Conner, C. J.; Sinn, E. Inorg. Chem. 1981, 20, 537-545.
10. (e) Kwiatkowski, M.; Kwiatkowski, E.; Olechnowicz, A.; Ho, D. M.; Deutsch, E. Inorg. Chim. Acta 1988, 150, 65-73.
11. (f) Bailey, N. A.; Fenton, D. E.; Moody, R.; Scrimshire, P. J.; Beloritzky, E.; Fries, P. H.; Latour, J.-M. J. Chem. Soc., Dalton Trans. 1988, 2817-2824.
12. (g) Agnus, Y.; Louis, R.; Metz, B.; Boudon, C.; Gisselbrecht, J. P.; Gross, M. Inorg. Chem. 1991, 30, 3155-3161.
13. (h) Sakai, K.; Yamada, Y.; Tsubomura, T.; Yabuki, M.; Yamaguchi, M. Inorg. Chem. 1996, 35, 542-544.
14. (i) Suh, M. P.; Han, M. Y.; Lee, J. H.; Min, K. S.; Hyeon, C. J. Am. Chem. Soc. 1998, 120, 3819-3820.
15. (j) Wang, Y. Y.; Zhou, L. J.; Shi, Q.; Shi, Q. Z.; Gao, Y. C.; Hou, X. Transition Met. Chem. 2002, 27, 145-148.
16. (k) Bian, H.-D.; Xu, J.-Y.; Gu, W.; Yan, S.-P.; Cheng, P.; Liao, D.-Z.; Jiang, Z.-H. Polyhedron, 2003, 22, 2927-2932.
17. (a) Hulsbergen, F. B.; ten Hoedt, R. W. M.; Verschoor, G. C.; Reedijk, J.; Spek, A. L. J. Chem. Soc., Dalton Trans. 1983, 539-545.
18. (b) Costes, J.-P.; Dahan, F.; Laurent, J.-P. Inorg. Chem. 1986, 25, 413-416.
19. (c) Angaroni, M.; Ardizzoia, G. A.; Beringhelli, T.; La Monica, G.; Gatteschi, D.; Masciocchi, N.; Moret, M. J. Chem. Soc., Dalton Trans. 1990, 3305-3309.
20. (d) Angaridis, P. A.; Baran, P.; Boča, R.; Cervantes-Lee, F.; Haase, W.; Mezei, G.; Raptis, R. G.; Werner, R. Inorg. Chem. 2002, 41, 2219-2228.
21. (a) Ferrer, S.; Lloret, F.; Bertomeu, I.; Alzuet, G.; Borrás, J.; García-Granda, S.; Liu-González, M.; Haasnoot, J. G. Inorg. Chem. 2002, 41, 5821-5830.
22. (b) Ferrer, S.; Haasnoot, J. G.; Reedijk, J.; Müller, E.; Biagini Cingi, M.; Lanfranchi, M.; Manotti Lanfredi, A. M.; Ribas, J. Inorg. Chem. 2000, 39, 1859-1867.
23. Liu, X.; de Miranda, M. P.; McInnes, E. J. L.; Kilner, C. A.; Halcrow, M. A. Dalton Trans. 2004, 59-64.
24. López-Sandoval, H.; Contreras, R.; Escuer, A.; Vicente, R.; Bernés, S.; Nöth, H.; Leigh, G. J.; Barba-Behrens, N. J. Chem. Soc., Dalton Trans. 2002, 2648-2653.
25. (a) Kozlowski, M. C.; Li, X.; Carroll, P. J.; Xu, Z. Organometallics 2002, 21, 4513-4522.
26. (b) Kodera, M.; Tachi, Y.; Kita, T.; Kobushi, H.; Sumi, Y.; Kano, K.; Shiro, M.; Koikawa, M.; Tokii, T.; Ohba, M.; Okawa, H. Inorg. Chem. 2000, 39, 226-234.
27. (a) Cage, B.; Cotton, F. A.; Dalal, N. S.; Hillard, E. A.; Rakvin, B.; Ramsey, C. M. J. Am. Chem. Soc. 2003, 125, 5270-5271.
28. (b) Clérac, R.; Cotton, F. A.; Dunbar, K. R.; Hillard, E. A.; Petrukhina, M. A.; Smucker, B. W. C. R. Acad. Sci. Paris, Chimie/Chemistry 2001, 4, 315-319.
29. (a) Padilla, J.; Gatteschi, D.; Chaudhuri, P. Inorg. Chim. Acta 1997, 260, 217-220.
30. (b) Chaudhuri, P.; Karpenstein, I.; Winter, M.; Butzlaff, C.; Bill, E.; Trautwein, A. X.; Flörke, U.; Haupt, H.-J. J. Chem. Soc., Chem. Commun. 1992, 321-322.
31. Machonkin, T. E.; Mukherjee, P.; Henson, M. J.; Stack, T. D. P.; Solomon, E. I. Inorg. Chim. Acta 2002, 341, 39-44.
32. (a) Cole, A. P.; Root, D. E.; Mukherjee, P.; Solomon, E. I.; Stack, T. D. P. Science 1996, 273, 1848-1850.
33. (b) Root, D. E.; Henson, M. J.; Machonkin, T.; Mukherjee, P.; Stack, T. D. P.; Solomon, E. I. J. Am. Chem. Soc. 1998, 120, 4982-4990.
34. (a) Solomon, E. I.; Chen, P.; Metz, M.; Lee, S.-K.; Palmer, A. E. Angew. Chem., Int. Ed. 2001, 40, 4570-4590.
35. (b) Solomon, E. I.; Sundaram, U. M.; Machonkin, T. E. Chem. Rev. 1996, 96, 2563-2605.
36. (c) Solomon, E. I.; Baldwin, M. J.; Lowery, M. D. Chem. Rev. 1992, 92, 521-542.
37. (a) Allendorf, M. D.; Spira, D. J.; Solomon, E. I. Proc. Natl. Acad. Sci. U.S.A. 1985, 82, 3063-3067.
38. (b) Spira-Solomon, D. J.; Allendorf, M. D.; Solomon, E. I. J. Am. Chem. Soc. 1986, 108, 5318-5328.
39. (c) Cole, J. L.; Tan, G. O.; Yang, E. K.; Hodgson, K. O.; Solomon, E. I. J. Am. Chem. Soc. 1990, 112, 2243-2249.
40. (d) Shin, W.; Sundaram, U. M.; Cole, J. L.; Zhang, H. H.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. J. Am. Chem. Soc. 1996, 118, 3202-3215.
41. (e) Lee, S.-K.; George, S. D.; Antholine, W. E.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. J. Am. Chem. Soc. 2002, 124, 6180-6193.
42. (a) Messerschmidt, A.; Ladenstein, R.; Huber, R.; Bolognesi, M.; Avigliano, L.; Petruzzelli, R.; Rossi, A.; Finazzi-Agró, A. J. Mol. Biol. 1992, 224, 179-205.
43. (b) Messerschmidt, A.; Luecke, H.; Huber, R. J. Mol. Biol. 1993, 230, 997-1014.
44. (c) Zaitseva, I.; Zaitsev, V.; Card, G.; Moshkov, K.; Bax, B.; Ralph, A.; Lindley, P. J. Biol. Inorg. Chem. 1996, 1, 15-23.
45. (d) Zaitsev, V. N.; Zaitseva, I.; Papiz, M.; Lindley, P. F. J. Biol. Inorg. Chem. 1999, 4, 579-587.
46. (e) Ducros, V.; Brzozowski, A. M.; Wilson, K. S.; Brown, S. H.; Ostergaard, P.; Schneider, P.; Yaver, D. S.; Pedersen, A. H.; Davies, G. J. Nat. Struct. Biol. 1998, 5, 310-316.
47. (f) Ducros, V.; Brzozowski, A. M.; Wilson, K. S.; Østergaard, P.; Schneider, P.; Svendson, A.; Davies, G. J. Acta Crystallogr. 2001, D57, 333-336.
48. (g) Bertrand, T.; Jolivalt, C.; Briozzo, P.; Caminade, E.; Joly, N.; Madzak, C.; Mougin, C. Biochemistry 2002, 41, 7325-7333.
49. (h) Piontek, K.; Antorini, M.; Choinowski, T. J. Biol. Chem. 2002, 277, 37663-37669.
50. (i) Hakulinen, N.; Kiiskinen, L.-L.; Kruus, K.; Saloheimo, M.; Paananen, A.; Koivula, A.; Rouvinen, J. Nat. Struct. Biol. 2002, 9, 601-605.
51. (j) Roberts, S. A.; Weichsel, A.; Grass, G.; Thakali, K.; Hazzard, J. T.; Tollin, G.; Rensing, C.; Montfort, W. R. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 2766-2771.
52. (k) Enguita, F. J.; Martins, L. O.; Henriques, A. O.; Carrondo, M. A. J. Biol. Chem. 2003, 278, 19416-19425.
53. Sinn, E. Coord. Chem. Rev. 1970, 5, 313-347.
54. (a) Griffith, J. S. Struct. Bond. 1972, 10, 87-126.
55. (b) Kokoszka, G. F.; Duerst, R. W. Coord. Chem. Rev. 1970, 5, 209-244.
56. Tsukerblat, B. S. Group Theory in Chemistry and Spectroscopy; Academic Press: London, 1994.
57. Tsukerblat, B. S.; Belinskii, M. I.; Fainzil'berg, V. E. Sov. Sci. Rev. B Chem. 1987, 9, 337-481.
58. (a) Clemente, J. M.; Palii, A. V.; Tsukerblat, B. S.; Georges, R. In Molecular Magnetism: From Molecular Assemblies to the Devices; Coronado, E., Delhaes, P., Gatteschi, D., Miller, J. S., Eds.; Kluwer: Dordrecht, 1996; pp 85-104.
59. (b) Fainzil'berg, V. E.; Belinskii, M. I.; Kuyavskaya, B. Ya.; Tsukerblat, B. S. Mol. Phys. 1985, 54, 799-812.
60. (c) Fainzil'berg, V. E.; Belinskii, M. I.; Tsukerblat, B. S. Mol. Phys. 1981, 44, 1195-1213.
61. (d) Belinskii, M. I.; Tsukerblat, B. S.; Ablov, A. V. Fiz. Tverd. Tela 1974, 16, 989-999.
62. Tsukerblat, B. S.; Kuyavskaya, B. Ya.; Belinskii, M. I.; Ablov, A. V.; Novotortsev, V. M.; Kalinnikov, V. T. Theor. Chim. Acta (Berl.) 1975, 38, 131-138.
63. Rakitin, Yu. V.; Yablokov, Yu. V.; Zelentsov, V. V. J. Magn. Reson. 1981, 43, 288-301.
64. Cannon, R. D.; White, R. P. Prog. Inorg. Chem. 1988, 36, 195-298.
65. Dzyaloshinsky, I. J. Phys. Chem. Solids 1958, 4, 241-255.
66. (a) Moriya, T. Phys. Rev. 1960, 120, 91-98.
67. (b) Moriya, T. In Magnetism; Rado, G. T., Suhl, H., Eds.; Academic Press: New York, 1963; Vol. 1, pp 85-125.
68. Nishimura, H.; Date, M. J. Phys. Soc. Jpn. 1985, 54, 395-399.
69. (a) Tiago de Oliveira, F.; Bominaar, E. L.; Hirst, J.; Fee, J. A.; Münck, E. J. Am. Chem. Soc. 2004, 126, 5338-5339.
70. (b) Sanakis, Y.; Macedo, A. L.; Moura, I.; Moura, J. J. G.; Papaefthymiou, V.; Münck, E. J. Am. Chem. Soc. 2000, 122, 11855-11863.
71. (c) Kauffmann, K. E.; Popescu, C. V.; Dong, Y.; Lipscomb, J. D.; Que, L., Jr.; Münck, E. J. Am. Chem. Soc. 1998, 120, 8739-8746.
72. Mirica, L. M.; Stack, T. D. P. Manuscript in preparation.
73. Cannon, R. D.; Jayasooriya, U. A.; Sowrey, F. E.; Tilford, C.; Little, A.; Bourke, J. P.; Rogers, R. D.; Vincent, J. B.; Kearley, G. J. Inorg. Chem. 1998, 37, 5675-5677.
74. Murao, T. Phys. Lett. 1974, 49A, 33-35.
75. (a) Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41-51.
76. (b) Te Velde, G.; Baerends, E. J. J. Comput. Phys. 1992, 99, 84-98.
77. Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200-1211.
78. Becke, A. D. J. Chem. Phys. 1986, 84, 4524-4529.
79. Perdew, J. P. Phys. Rev. B 1986, 33, 8822-8824.
80. Noodleman, L. J. Chem. Phys. 1981, 74, 5737-5743.
81. A detailed study of the excited-state MCD spectrum of TrisOH is in progress.
82. Solomon, E. I.; Hanson, M. A. In Inorganic Electronic Structure and Spectroscopy; Solomon, E. I., Lever, A. B. P., Eds.; John Wiley & Sons: New York, 1999; pp 1-129.
83. Solomon, E. I.; Pavel, E. G.; Loeb, K. E.; Campochiaro, C. Coord. Chem. Rev. 1995, 144, 369-460.
84. (a) Solomon, E. I.; Brunold, T. C.; Davis, M. I.; Kemsley, J. N.; Lee, S.-K. Lehnert, N.; Neese, F.; Skulan, A. J.; Yang, Y.-S.; Zhou, J. Chem. Rev. 2000, 100, 235-349.
85. (b) Solomon, E. I.; Decker, A.; Lehnert, N. Proc. Natl. Acad. Sci. U.S.A. 2003, 100, 3589-3594.
86. (c) Solomon, E. I. Inorg. Chem. 2001, 40, 3656-3669.
87. Neese, F.; Solomon, E. I. Inorg. Chem. 1999, 38, 1847-1865.
88. (a) Stephens, P. J. Annu. Rev. Phys. Chem. 1974, 25, 201-232.
89. (b) Piepho, S. B.; Schatz, P. N. Group Theory in Spectroscopy with Applications to Magnetic Circular Dichroism; John Wiley & Sons: New York, 1983.
90. Pavel, E. G.; Kitajima, N.; Solomon, E. I. J. Am. Chem. Soc. 1998, 120, 3949-3962.
91. y) ≈ 0.
92. tot = 112 states.
93. The Zeeman energy levels are linearly dependent on H only when θ = 0° (Scheme 2 (left)). At this limit, the nonnesting behavior would be expected in VTVH MCD, which is the case for TrisOH in the low-temperature region (1.78 to 20 K). If θ ≠ 0°, nesting would be observed even at this low-temperature region. Thus, the assignment of the 330 nm band as x,y-polarized is validated.
94. Belinsky, M. I. Inorg. Chem. 2004, 43, 739-746.
95. (a) Gatteschi, D.; Bencini, A. In Magneto-Structural Correlations in Exchange Coupled Systems; Willett, R. D., Gatteschi, D., Kahn, O., Eds.; D. Reidel: Dordrecht, The Netherlands, 1985; pp 241-268.
96. (b) Bencini, A.; Gatteschi, D. Electron Paramagnetic Resonance of Exchange Coupled Systems; Springer-Verlag: Berlin, 1990.
97. y) would have negligible contributions in the antisymmetric exchange interaction.
98. Details of the broken-symmetry wave functions from DFT electronic calculations will be presented in ref 37.
99. Ross, P. K.; Allendorf, M. D.; Solomon, E. I. J. Am. Chem. Soc. 1989, 11, 4009-4021.
100. (a) Banci, L.; Bencini, A.; Gatteschi, D. J. Am. Chem. Soc. 1983, 105, 761-764.
101. (b) Banci, L.; Bencini, A.; Gatteschi, D. Inorg. Chem. 1984, 23, 2138-2141.
102. (c) Charlot, M.-F.; Joumaux, Y.; Kahn, O.; Bencini, A.; Gatteschi, D.; Zanchini, C. Inorg. Chem. 1986, 25, 1060-1063.