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Synthesis, Crystal Structure, Magnetic, and Electron Paramagnetic Resonance Properties of a Spiroconjugated Biradical. Evidence for Spiroconjugation Exchange Pathway

Frank, Natia L. and Clérac, Rodolphe and Sutter, Jean-Pascal and Daro, Nathalie and Kahn, Olivier and Coulon, Claude and Green, Michael T. and Golhen, Stéphane and Ouahab, Lahcène (2000) Synthesis, Crystal Structure, Magnetic, and Electron Paramagnetic Resonance Properties of a Spiroconjugated Biradical. Evidence for Spiroconjugation Exchange Pathway. Journal of the American Chemical Society, 122 (9). pp. 2053-2061. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20170515-134652976

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Abstract

A spiroconjugated nitronyl nitroxide biradical, 6,6‘-(4,4,5,5-tetramethylimidazolidine-3-oxide-1-oxyl)-3,3,3‘,3‘-tetramethyl-1,1‘-spirobisindane (1), has been prepared by functionalization of a 3,3,3‘,3‘-tetramethyl-1,1‘-spirobisindane framework followed by Ullman condensation and subsequent oxidation. The biradical crystallizes in the monoclinic space group C2/c with four molecules in the unit cell of dimensions a = 24.861(10) Å, b = 12.129(3) Å, and c = 12.258(6) Å. X-ray analysis of a blue-plate single crystal has revealed dihedral angles of 28° between the nitronyl nitroxide moiety and aromatic ring with intramolecular through space radical−radical distances of 8.25 and 10.11 Å. In the solid state, the temperature dependence of the molar magnetic susceptibility reveals antiferromagnetic interactions. These interactions are best fit using a pair model, affording the value J = −4.0 cm^(-1) where J is the interaction parameter appearing in the spin Hamiltonian H = −JS_1·S_2. The field dependence of the magnetization measured at 2 K is consistent with a pair model. Frozen matrix EPR spectra of biradical 1 in CH_2Cl_2 at 100 K shows a half field transition at 1700 G. Temperature dependence of the half field transition intensity has been found to be consistent with a ground singlet state and thermally accessible triplet state. The magnetic interaction observed in the solid state is also observed in solution. Thus, room-temperature solution spectra display a nine-line pattern, with hyperfine coupling to four “equivalent” nitrogen atoms and a hyperfine coupling constant a_N = 3.8 G. Temperature dependence of the solution EPR spectra of biradical 1 displays alternating line width effects caused by conformational dynamics in solution. This behavior has been attributed to modulation of exchange and hyperfine interactions most likely caused by rotational motion about the nitronyl nitroxide−phenyl bond. Biradical 1 therefore exists as a ground-state singlet with a thermally accessible triplet at ca. 4 cm^(-1) higher in energy with a conformational dependence of intramolecular exchange in solution. This coupling may present evidence for spiroconjugation as an exchange pathway. Density functional calculations (B3/6-311G(D)) have been performed to investigate this possibility.


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http://dx.doi.org/10.1021/ja993071aDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja993071aPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja993071aPublisherSupporting Information
Additional Information:© 2000 American Chemical Society. Received August 23, 1999. Publication Date (Web): February 17, 2000. N.L.F. gratefully acknowledges the CNRS for a postdoctoral research fellowship. N.L.F also thanks Prof. P. T Narasimhan for invaluable discussions and Prof. B. Bales for assistance with additional EPR measurements.
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Record Number:CaltechAUTHORS:20170515-134652976
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170515-134652976
Official Citation:Synthesis, Crystal Structure, Magnetic, and Electron Paramagnetic Resonance Properties of a Spiroconjugated Biradical. Evidence for Spiroconjugation Exchange Pathway Natia L. Frank, Rodolphe Clérac, Jean-Pascal Sutter, Nathalie Daro, Olivier Kahn, Claude Coulon, Michael T. Green, Stéphane Golhen, and Lahcène Ouahab Journal of the American Chemical Society 2000 122 (9), 2053-2061 DOI: 10.1021/ja993071a
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77461
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:16 May 2017 19:37
Last Modified:16 May 2017 19:37

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