Citation: MA De-Yun, XIAO Jun-Xia, GUO Hai-Fu, LIANG Yun-Qiu, YAN Jing-Jing, LIN Wei-Jie, DING Wan-Qiu. Magnetic Properties in Mononuclear Gadolinium(III) and Terbium(III) Complexes Based on Ethoxylphenyl-substituted Nitronyl Nitroxide Radical and Hexafluoroacetylacetonate Ligand[J]. Chinese Journal of Structural Chemistry, ;2016, 35(3): 361-370. doi: 10.14102/j.cnki.0254-5861.2011-0885 shu

Magnetic Properties in Mononuclear Gadolinium(III) and Terbium(III) Complexes Based on Ethoxylphenyl-substituted Nitronyl Nitroxide Radical and Hexafluoroacetylacetonate Ligand

1.
School of Chemistry and Chemical Engineering, Zhaoqing University, Zhaoqing 526061, China

Corresponding author: MA De-Yun,
Received Date: 9 July 2015
Available Online: 11 November 2015
Fund Project: the Natural Science Foundation of Guangdong Province (2015A030310407) (pdjh2015a0562) the Natural Science Foundation of Zhaoqing University (201532) (2015A030310407)the Project of Provincial Key Platform of Guangdong Province (2014KTSPT040) (201532)

Two new lanthanide complexes with ethoxybenzene-substituted nitronyl nitroxide radical (NIT-C₈H₉O) and hexafluoroacetylacetonate (hfac) ligand, [Gd(NIT-C₈H₉O)₂(hfac)₃]·C₇H₁₆ (1) and [Tb(NIT-C₈H₉O)₂(hfac)₃]·C₇H₁₆ (2), have been successfully synthesized and characterized by IR spectroscopy, elemental analyses, thermogravimetry analyses, and single-crystal X-ray diffraction. Both 1 and 2 exhibit a mononuclear structure in which the nitronyl nitroxide radical and hfac ligand act as monodentate and bidentate chelating modes, respectively. Magnetic studies show that ferromagnetic interactions (between intramolecular Gd and radical) and antiferromagnetic interactions (between the intramolecular radicals) coexist in complex 1. No obvious frequency dependent out-of-phase signals were observed in complex 2.
- lanthanide complexes,
- characterization,
- radicals,
- magnetism
1. [1]
  (1) Troiani, F.; Affronte, M. Molecular spins for quantum information technologies. Chem. Soc. Rev. 2011, 40, 3119-3129.
2. [2]
  (2) Leuenberger, M. N.; Loss, D. Quantum computing in molecular magnets. Nature 2001, 410, 789-793.
3. [3]
  (3) Ganzhorn, M.; Klyatskaya, S.; Ruben, M.; Wernsdorfer, W. Strong spin-phonon coupling between a single-molecule magnet and a carbon nanotube nanoelectromechanical system. Nature Nanotech. 2012, 8, 165-169.
4. [4]
  (4) Bogani, L.; Wernsdorfer, W. Molecular spintronics using single-molecule magnets. Nature Mater. 2008, 7, 179-186.
5. [5]
  (5) Lin, S. Y.; Wernsdorfer, W.; Ungur, L.; Powell, A. K.; Guo, Y. N.; Tang, J.; Zhao, L.; Chibotaru, L. F.; Zhang, H. J. Coupling Dy₃ triangles to maximize the toroidal moment. Angew. Chem. Int. Ed. 2012, 51, 12939-12943.
6. [6]
  (6) Ungur, L.; Lin, S. Y.; Tang, J. K.; Chibotaru, L. F. Single-molecule toroics in ising-type lanthanide molecular clusters. Chem. Soc. Rev. 2014, 43, 6894-6905.
7. [7]
  (7) Mei, X. L.; Liu, R. N.; Wang, C.; Yang, P. P.; Li, L. C.; Liao, D. Z. Modulating spin dynamics of cyclic Ln^III-radical complexes (Ln^III = Tb, Dy) by using phenyltrifluoroacetylacetonate coligand. Dalton Trans. 2012, 41, 2904-2909.
8. [8]
  (8) Bernot, K.; Pointillart, F.; Rosa, P.; Etienne, M.; Sessoli, R.; Gatteschi, D. Single molecule magnet behaviour in robust dysprosium-biradical complexes. Chem. Comm. 2010, 46, 6458-6460.
9. [9]
  (9) Fatila, E. M.; Rouzieres, M.; Jennings, M. C.; Lough, A. J.; Clerac, R.; Preuss, K. E. Fine-tuning the single-molecule magnet properties of a [Dy(III)-radical]₂ pair. J. Am. Chem. Soc. 2013, 135, 9596-9599.
10. [10]
  (10) Demir, S.; Zadrozny, J. M.; Nippe, M.; Long, J. R. Exchange coupling and magnetic blocking in bipyrimidyl radical-bridged dilanthanide complexes. J. Am. Chem. Soc. 2012, 134, 18546-18549.
11. [11]
  (11) Escobar, L. B. L.; Gueder, G. P.; Soriano, S.; Speziali, N. L.; Jordao, A. K.; Cunha, A. C.; Ferreira, V. F.; Maxim, C.; Novak, M. A.; Andruh, M.; Vaz, M. G. F. New families of hetero-tri-spin 2p-3d-4f complexes: synthesis, crystal structures, and magnetic properties. Inorg. Chem. 2014, 53, 7508-7517.
12. [12]
  (12) Wang, X. F.; Hu, P.; Li, Y. G.; Li, L. C. Construction of nitronyl nitroxide-based 3d-4f clusters: structure and magnetism. Chem. Asian J. 2015, 10, 325-328.
13. [13]
  (13) Li, L. L.; Liu, S.; Zhang, Y.; Shi, W.; Cheng, P. Three new mononuclear tri-spin lanthanide nitronyl nitroxide radical compounds: syntheses, structures and magnetic properties. Dalton Trans. 2015, 44, 6118-6125.
14. [14]
  (14) Ullman, E. F.; Osiecki, J. H.; Boocock, D. G. B.; Darcy, R. Stable free radicals. X. Nitronyl nitroxide monoradicals and biradicals as possible small molecule spin labels. J. Am. Chem. Soc. 1972, 94, 7049-7059.
15. [15]
  (15) Bruker. APEXII software, Version 6.3.1, Bruker AXS Inc, Madison, Wisconsin, USA (2004).
16. [16]
  (16) Parkin, S.; Moezzi, B.; Hope, H. XABS2: an empirical absorption correction program. J. Appl. Cryst. 1995, 28, 53-56.
17. [17]
  (17) Sheldrick, G. M. A short history of SHELX Acta. Cryst. 2008, A64, 112-122.
18. [18]
  (18) Spek, A. L. PLATON, A Multipurpose Crystallographic Tool. Utrecht University: Utrecht, The Netherlands (2005).
19. [19]
  (19) Wang, X. L. Five new tri-spin lanthanide-nitronyl nitroxide (Ln^III = Gd^III, Tb^III, Dy^III, Ho^III, Er^III) complexes: structures and magnetic properties. Inorg. Chim. Acta 2012, 387, 20-24.
20. [20]
  (20) Benelli, C.; Caneschi, A.; Gatteschi, D.; Laugier, J.; Rey, P. Structure and magnetic properties of a gadolinium hexafluoroacetylacetonate adduct with the radical 4, 4, 5, 5-tetramethyl-2-phenyl-4, 5-dihydro-1H-imidazole 3-oxide 1-oxyl. Angew. Chem. Int. Ed. 1987, 26, 913-917.
21. [21]
  (21) Kahn, M. L.; Sutter J. P.; Golhen, S.; Guionneau, P.; Ouahab, L.; Kahn O.; Chasseau, D. Systematic investigation of the nature of the coupling between a Ln(III) ion (Ln = Ce(III) to Dy(III)) and its aminoxyl radical ligands. Structural and magnetic characteristics of a series of {Ln(organic radical)₂} compounds and the related {Ln(Nitrone)₂} derivatives. J. Am. Chem. Soc. 2000, 122, 3413-3421.
22. [22]
  (22) Meng, Z. S.; Liu, J. L.; Leng, J. D.; Guo, F. S.; Tong, M. L. Linear trinuclear Mn^II-Ln^III-Mn^II clusters via the “compartmentalized ligand” approach: synthesis, structures and magnetic properties. Polyhedron 2011, 30, 3095-3099.
23. [23]
  (23) Hu, P.; Sun, Z.; Wang, X.; Li, L.; Liao, D.; Luneau, D. Magnetic relation in mononuclear Tb complex involving a nitronyl nitroxide ligand. New J. Chem. 2014, 38, 4716-4721.
24. [24]
  (24) Du, F. X.; Hu, P.; Gao, Y. Y.; Xiao, F. P.; Wu, Y. N. A hydroxyl-containing nitronyl nitroxide radical and its Gd(III), Tb(III), Dy(III) complexes: synthesis, structure and magnetic properties. Inorg. Chem. Commun. 2014, 48, 166-170.
25. [25]
  (25) Zhang, C. X.; Qiao, X. M.; Kong, Y. K.; Wang, B.; Zhang, Y. Y.; Wang, Q. L. Two Lanthanide-nitronyl nitroxide radicals compounds with slow magnetic relaxation behavior. Journal of Molecular Structure 2015, 1081, 348-354.
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