Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter (O) November 4, 2016

Multifrequency Multiresonance EPR Investigation of Halogen-bonded Complexes Involving Neutral Nitroxide Radicals

  • Thomas Lohmiller , Mahesh A. Vibhute , Wolfgang Lubitz and Anton Savitsky EMAIL logo


Halogen-bonded complexes with neutral nitroxide radicals as the Lewis base have been investigated in liquid and frozen solutions by multifrequency CW and pulse EPR spectroscopies, including ENDOR and ELDOR-detected NMR (EDNMR) techniques. The non-covalent interaction with iodopentafluorobenzene as halogen-bond donor is shown to affect a variety of EPR parameters of the stable nitroxide radicals. In liquid solution, only bulk effects on the EPR signal, i.e. isotropic g value, isotropic 14N hyperfine coupling and linewidth, are observed. Experiments on frozen solutions allow for a more in-depth dissection of complexing effects. W-band EPR spectra at cryogenic temperatures exhibit multiple signal components of different 14N hyperfine interactions and spectral widths. This demonstrates the coexistence of several halogen-bonded complexes that differ in donor-acceptor binding geometries. These complexes have different relaxation properties, which allow for their spectral discrimination. 19F ENDOR experiments prove the origin of these effects to be different specific intermolecular interactions rather than a consequence of changes in the solvation environment. The EPR spectra yet reveal a strong influence of solvent composition on the amount of the various complexes formed. The introduced methodology for the characterization of such adducts improves our understanding of halogen bonding and could be helpful in the development of tailor-made donors and complexes for specific applications.

Dedicated to: Kev Salikhov on the occasion of his 80th birthday.


This work was supported by the Max-Planck-Gesellschaft and the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft (DFG).


1. P. Metrangolo, G. Resnati, (Eds.), Halogen Bonding: Fundamentals and Applications, Springer-Verlag, Berlin, Heidelberg (2008).Search in Google Scholar

2. P. Metrangolo, G. Resnati, Chem. – Eur. J. 7 (2001) 2511.10.1002/1521-3765(20010618)7:12<2511::AID-CHEM25110>3.0.CO;2-TSearch in Google Scholar

3. P. Metrangolo, H. Neukirch, T. Pilati, G. Resnati, Acc. Chem. Res. 38 (2005) 386.10.1021/ar0400995Search in Google Scholar

4. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, Angew. Chem. Int. Ed. 47 (2008) 6114.10.1002/anie.200800128Search in Google Scholar

5. M. Fourmigue, Curr. Opin. Solid State Mater. Sci. 13 (2009) 36.10.1016/j.cossms.2009.05.001Search in Google Scholar

6. A. C. Legon, Phys. Chem. Chem. Phys. 12 (2010) 7736.10.1039/c002129fSearch in Google Scholar

7. S. H. Jungbauer, S. Schindler, F. Kniep, S. M. Walter, L. Rout, S. M. Huber, Synlett 24 (2013) 2624.10.1055/s-0033-1338981Search in Google Scholar

8. S. Schindler, S. M. Huber, In: Halogen Bonding II: Impact on Materials Chemistry and Life Sciences, (Eds. P. Metrangolo and G. Resnati), volume 359, Springer International Publishing, Cham (2015), p. 167.Search in Google Scholar

9. S. H. Jungbauer, S. M. Huber, J. Am. Chem. Soc. 137 (2015) 12110.10.1021/jacs.5b07863Search in Google Scholar

10. P. Politzer, J. S. Murray, T. Clark, Phys. Chem. Chem. Phys. 12 (2010) 7748.10.1039/c004189kSearch in Google Scholar

11. O. Hassel, J. Hvoslef, Acta Chem. Scand. 8 (1954) 873.10.3891/acta.chem.scand.08-0873Search in Google Scholar

12. P. Auffinger, F. A. Hays, E. Westhof, P. S. Ho, Proc. Natl. Acad. Sci. U. S. A. 101 (2004) 16789.10.1073/pnas.0407607101Search in Google Scholar

13. I. Morishima, T. Inubushi, T. Yonezawa, K. Endo, Chem. Phys. Lett. 14 (1972) 372.10.1016/0009-2614(72)80136-2Search in Google Scholar

14. I. Morishima, T. Yonezawa, K. Endo, T. Inubushi, K. Goto, J. Am. Chem. Soc. 94 (1972) 4812.10.1021/ja00769a003Search in Google Scholar

15. I. Morishima, T. Inubushi, T. Yonezawa, J. Am. Chem. Soc. 98 (1976) 3808.10.1021/ja00429a012Search in Google Scholar

16. Y. Hosokoshi, M. Tamura, K. Nozawa, S. Suzuki, M. Kinoshita, H. Sawa, R. Kato, Synth. Met. 71 (1995) 1795.10.1016/0379-6779(94)03054-ASearch in Google Scholar

17. F. Iwasaki, J. H. Yoshikawa, H. Yamamoto, E. Kan-Nari, K. Takada, M. Yasui, T. Ishida, T. Nogami, Acta Crystallogr. Sect. B: Struct. Sci. 55 (1999) 231.10.1107/S0108768198012786Search in Google Scholar

18. I. M. Ganiev, Q. K. Timerghazin, A. F. Khalizov, N. M. Andriyashina, V. V. Shereshovets, L. B. Volodarsky, G. A. Tolstikov, Tetrahedron Lett. 40 (1999) 4737.10.1016/S0040-4039(99)00837-0Search in Google Scholar

19. I. M. Ganiev, Q. K. Timerghazin, A. F. Khalizov, V. V. Shereshovets, A. I. Grigor’ev, G. A. Tolstikov, J. Phys. Org. Chem. 14 (2001) 38.10.1002/1099-1395(200101)14:1<38::AID-POC334>3.0.CO;2-ZSearch in Google Scholar

20. K. Boubekeur, J. L. Syssa-Magale, P. Palvadeau, B. Schollhorn, Tetrahedron Lett. 47 (2006) 1249.10.1016/j.tetlet.2005.12.088Search in Google Scholar

21. V. Mugnaini, C. Punta, R. Liantonio, P. Metrangolo, F. Recupero, G. Resnati, G. F. Pedulli, M. Lucarini, Tetrahedron Lett. 47 (2006) 3265.10.1016/j.tetlet.2006.03.033Search in Google Scholar

22. G. R. Hanson, P. Jensen, J. McMurtrie, L. Rintoul, A. S. Micallef, Chem. – Eur. J. 15 (2009) 4156.10.1002/chem.200801920Search in Google Scholar

23. G. M. Espallargas, A. Recuenco, F. M. Romero, L. Brammer, S. Libri, CrystEngComm 14 (2012) 6381.10.1039/c2ce26131fSearch in Google Scholar

24. P. Cimino, M. Pavone, V. Barone, J. Phys. Chem. A 111 (2007) 8482.10.1021/jp073567bSearch in Google Scholar PubMed

25. C. Cavallotti, P. Metrangolo, F. Meyer, F. Recupero, G. Resnati, J. Phys. Chem. A 112 (2008) 9911.10.1021/jp803685rSearch in Google Scholar PubMed

26. A. Savitsky, M. Plato, K. Möbius, Appl. Magn. Reson. 37 (2010) 415.10.1007/s00723-009-0064-9Search in Google Scholar

27. A. Nalepa, K. Möbius, W. Lubitz, A. Savitsky, J. Magn. Reson. 242 (2014) 203.10.1016/j.jmr.2014.02.026Search in Google Scholar PubMed

28. E. Bordignon, A. I. Nalepa, A. Savitsky, L. Braun, G. Jeschke, J. Phys. Chem. B 119 (2015) 13797.10.1021/acs.jpcb.5b04104Search in Google Scholar PubMed

29. A. Savitsky, A. A. Dubinskii, M. Plato, Y. A. Grishin, H. Zimmermann, K. Möbius, J. Phys. Chem. B 112 (2008) 9079.10.1021/jp711640pSearch in Google Scholar PubMed

30. K. Möbius, A. Savitsky, A. Schnegg, M. Plato, M. Fuchs, Phys. Chem. Chem. Phys. 7 (2005) 19.10.1039/B412180ESearch in Google Scholar PubMed

31. K. Möbius, A. Savitsky, High-Field EPR Spectroscopy on Proteins and their Model Systems, RSC Publishing, Cambridge, UK (2008).Search in Google Scholar

32. O. Burghaus, M. Rohrer, T. Götzinger, M. Plato, K. Möbius, Meas. Sci. Technol. 3 (1992) 765.10.1088/0957-0233/3/8/013Search in Google Scholar

33. E. L. Hahn, Phys. Rev. 80 (1950) 580.10.1103/PhysRev.80.580Search in Google Scholar

34. L. G. Rowan, E. L. Hahn, W. B. Mims, Phys. Rev. 137 (1965) A61.10.1103/PhysRev.137.A61Search in Google Scholar

35. P. Schosseler, T. Wacker, A. Schweiger, Chem. Phys. Lett. 224 (1994) 319.10.1016/0009-2614(94)00548-6Search in Google Scholar

36. W. B. Mims, Proc. R. Soc. Lond. A 283 (1965) 452.10.1098/rspa.1965.0034Search in Google Scholar

37. R. Improta, V. Barone, Chem. Rev. 104 (2004) 1231.10.1021/cr960085fSearch in Google Scholar

38. T. Kawamura, S. Matsunam, T. Yonezawa, Bull. Chem. Soc. Jpn. 40 (1967) 1111.10.1246/bcsj.40.1111Search in Google Scholar

39. O. H. Griffith, P. J. Dehlinge, S. P. Van, J. Membr. Biol. 15 (1974) 159.10.1007/BF01870086Search in Google Scholar

40. R. Owenius, M. Engstrom, M. Lindgren, M. Huber, J. Phys. Chem. A 105 (2001) 10967.10.1021/jp0116914Search in Google Scholar

41. P. Franchi, M. Lucarini, P. Pedrielli, G. F. Pedulli, ChemPhysChem 3 (2002) 789.10.1002/1439-7641(20020916)3:9<789::AID-CPHC789>3.0.CO;2-ZSearch in Google Scholar

42. H. Lefebvre-Brion, R. W. Field, Perturbations in the Spectra of Diatomic Molecules, Academic Press, Inc., Orlando (1986).Search in Google Scholar

43. M. Engstrom, R. Owenius, O. Vahtras, Chem. Phys. Lett. 338 (2001) 407.10.1016/S0009-2614(01)00311-6Search in Google Scholar

44. B. C. Gilbert, R. O. C. Norman, J. Chem. Soc. B (1967) 981.10.1039/j29670000981Search in Google Scholar

45. H. Sillescu, Mol. Phys. 14 (1968) 381.10.1080/00268976800100461Search in Google Scholar

46. E. F. Ullman, L. Call, J. H. Osiecki, J. Org. Chem. 35 (1970) 3623.10.1021/jo00836a008Search in Google Scholar

47. N. Cox, W. Lubitz, A. Savitsky, Mol. Phys. 111 (2013) 2788.10.1080/00268976.2013.830783Search in Google Scholar

48. N. Cox, A. Nalepa, M. E. Pandelia, W. Lubitz, A. Savitsky, in: Methods in Enzymology, (Eds. P. Z. Qin and K. Warncke), volume 563, Elsevier, Amsterdam (2015), p. 211.Search in Google Scholar

Received: 2016-7-20
Accepted: 2016-10-9
Published Online: 2016-11-4
Published in Print: 2017-4-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 4.3.2024 from
Scroll to top button