Field-Induced Dysprosium Single-Molecule Magnet Involving a Fused o-Semiquinone-Extended-Tetrathiafulvalene-o-Semiquinone Bridging Triad
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis
2.2. Crystal Structure Description of {[Dy(hfac)3(L)]·2C6H14}n (1)
2.3. Infrared Spectroscopy
2.4. Absorption Spectroscopy
2.5. Magnetic Properties
3. Experimental Section
3.1. Synthesis
3.2. Synthesis of Complex {[Dy(hfac)3(L)]·2C6H14}n (1)
3.3. Crystallography
3.4. Physical Measurements
4. Conclusions and Outlook
Supplementary Materials
Author Contributions
Acknowledgments
Conflicts of Interest
References
- Benelli, C.; Gatteschi, D. Magnetism of Lanthanides in Molecular Materials with Transition-Metal Ions and Organic Radicals. Chem. Rev. 2002, 102, 2369–2388. [Google Scholar] [CrossRef] [PubMed]
- Sessoli, R.; Powell, A.K. Strategies towards single molecule magnets based on lanthanide ions. Coord. Chem. Rev. 2009, 253, 2328–2341. [Google Scholar] [CrossRef]
- Woodruff, D.N.; Winpenny, R.E.P.; Layfield, R.A. Lanthanide single-molecule magnets. Chem. Rev. 2013, 113, 5110–5148. [Google Scholar] [CrossRef] [PubMed]
- Bünzli, J.-C.G.; Piguet, C. Taking advantage of luminescent lanthanide ions. Chem. Soc. Rev. 2005, 34, 1048–1077. [Google Scholar] [CrossRef] [PubMed]
- Li, X.-L.; Chen, C.-L.; Xiao, H.-P.; Wang, A.-L.; Liu, C.-M.; Zheng, X.; Gao, L.-J.; Yanga, X.-G.; Fang, S.-M. Luminescent, magnetic and ferroelectric properties of noncentrosymmetric chain-like complexes composed of nine-coordinated lanthanide ions. Dalton Trans. 2013, 42, 15317–15325. [Google Scholar] [CrossRef] [PubMed]
- Soussi, K.; Jung, J.; Pointillart, F.; Le Guennic, B.; Lefeuvre, B.; Golhen, S.; Cador, O.; Guyot, Y.; Maury, O.; Ouahab, L. Magnetic and photo-physical inverstigations into DyIII and YbIII complexes involving tetrathiafulvalene ligand. Inorg. Chem. Front. 2015, 2, 1105–1117. [Google Scholar] [CrossRef]
- Cucinotta, G.; Perfetti, M.; Luzon, J.; Etienne, M.; Car, P.E.; Caneschi, A.; Calvez, G.; Bernot, K.; Sessoli, R. Magnetic Anisotropy in a Dysprosium/DOTA Single-Molecule Magnet: Beyond Simple Magneto-Structural Correlations. Angew. Chem. Int. Ed. 2012, 51, 1606–1610. [Google Scholar] [CrossRef] [PubMed]
- Long, J.; Rouquette, J.; Thibaud, J.-M.; Ferreira, R.A.S.; Carlos, L.D.; Donnadieu, B.; Vieru, V.; Chibotaru, L.F.; Konczewicz, L.; Haines, J.; et al. A high-Temperature Molecular Ferroelectric Zn/Dy Complex Exhibiting Single-Ion-Magnet Behavior and Lanthanide Luminescence. Angew. Chem. Int. Ed. 2015, 54, 2236–2240. [Google Scholar] [CrossRef] [PubMed]
- Lin, S.-Y.; Wang, C.; Zhao, L.; Wua, J.; Tang, J. Chiral mononuclear lanthanide complexes and the field-induced single-ion magnet behavior of a Dy analogue. Dalton Trans. 2015, 44, 223–229. [Google Scholar] [CrossRef] [PubMed]
- Ou-Yang, J.-K.; Saleh, N.; Fernandez Garcia, G.; Norel, L.; Pointillart, F.; Guizouarn, T.; Cador, O.; Totti, F.; Ouahab, L.; Crassous, J.; et al. Improved slow magnetic relaxation in optically pure helicene-based DyIII single molecule magnets. Chem. Commun. 2016, 52, 14474–14477. [Google Scholar] [CrossRef] [PubMed]
- Pointillart, F.; Le Guennic, B.; Golhen, S.; Cador, O.; Ouahab, L. Slow magnetic relaxation in radical cation tetrathiafulvalene-based lanthanide(III) dinuclear complexes. Chem. Commun. 2013, 49, 11632–11634. [Google Scholar] [CrossRef] [PubMed]
- Pointillart, F.; Golhen, S.; Cador, O.; Ouahab, L. Slow Magnetic Relaxation in a Redox-Active Tetrathiafulvalene-Based Ferromagnetic Dusprosium Complex. Eur. J. Inorg. Chem. 2014, 2014, 4558–4563. [Google Scholar] [CrossRef]
- Rovira, C.; Hudhomme, P. Intramolecular electron transfer mediated by a tetrathiafulvalene bridge in a purely organic mixed-valence system. Angew. Chem. Int. Ed. 2003, 42, 2765–2768. [Google Scholar]
- Dumur, F.; Gautier, N.; Gallego-Planas, N.; Sahin, Y.; Levillain, E.; Mercier, N.; Hudhomme, P. Novel Fused D-A Dyad and A-D-A Triad Incorporating Tetrathiafulvalene and p-Benzoquinone. J. Org. Chem. 2004, 69, 2164–2177. [Google Scholar] [CrossRef] [PubMed]
- Kuropatov, V.; Klementieva, S.; Fukin, G.; Mitin, A.; Ketlov, S.; Budnikova, Y.; Cherkasov, V.; Abakumov, G. Novel method for the synthesis of functionalized tetrathiafulvalenes, an acceptor–donor–acceptor molecule comprising of two o-quinone moieties linked by a TTF bridge. Tetrahedron 2010, 66, 7605–7611. [Google Scholar] [CrossRef]
- Abakumov, G.A.; Nevodchikov, V.I. Thermomechanical and Photomechanical Effects in the Crystals of Complexes with Free Radicals. Dokl. Akad. Nauk SSSR 1982, 266, 1407–1410. [Google Scholar]
- Abakumov, G.A.; Nevodchikov, V.I.; Cherkasov, V.K. A reversible intramolecular metal-ligand electron transfer in o-semiquinonate rhodium complexes. A redox-isomerism in paramagnetic metal complexes. Dokl. Akad. Nauk SSSR 1984, 278, 641–645. [Google Scholar]
- Perepichka, D.F.; Bryce, M. Molecules with exceptionally small HOMO–LUMO gaps. Angew. Chem. Int. Ed. 2005, 44, 5370–5373. [Google Scholar] [CrossRef] [PubMed]
- Pointillart, F.; Klementieva, S.; Kuropatov, V.; Le Gal, Y.; Golhen, S.; Cador, O.; Cherkasov, V.; Ouahab, L. A single molecule magnet behavior in a D3h symmetry Dy(III) complex involving a quinone-tetrathiafulvalene-quinone bridge. Chem. Commun. 2012, 48, 714–716. [Google Scholar] [CrossRef] [PubMed]
- Pointillart, F.; Kuropatov, V.; Mitin, A.; Maury, O.; Le Gal, Y.; Golhen, S.; Cador, O.; Cherkasov, V.; Ouahab, L. Lanthanide-Based Dinuclear Complexes Involving an o-Quinone-Tetrathiafulvalene-o-Quinone Bridging Ligand: X-ray Structures, Magnetic and Photophysical Properties. Eur. J. Inorg. Chem. 2012, 2012, 4708–4718. [Google Scholar] [CrossRef]
- Yamashita, Y.; Kobayashi, Y.; Miyashi, T. p-Quinodimethane Analogues of Tetrathiafulvalene. Angew. Chem. Int. Ed. 1989, 28, 1052–1053. [Google Scholar] [CrossRef]
- Chalkov, N.O.; Cherkasov, V.K.; Abakumov, G.A.; Romanenko, G.V.; Ketkov, S.Y.; Smolyaninov, I.V.; Starikov, A.G.; Kuropatov, V.A. Compactly Fused o-Quinone-Extended Tetrathiafulvalene-o-Quinone Triad—A Redox-Amphoteric Ligand. Eur. J. Org. Chem. 2014, 2014, 4571–4576. [Google Scholar] [CrossRef]
- Chalkov, N.O.; Cherkasov, V.K.; Abakumov, G.A.; Starikov, A.G.; Kuropatov, V.A. Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study. Beilstein J. Org. Chem. 2016, 12, 2450–2456. [Google Scholar] [CrossRef] [PubMed]
- Llunell, M.; Casanova, D.; Cirera, J.; Bofill, J.M.; Alemany, P.; Alvarez, S. SHAPE (v. 2.1); University of Barcelona: Barcelona, Spain, 2013. [Google Scholar]
- Pointillart, F.; Cauchy, T.; Maury, O.; Le Gal, Y.; Golhen, S.; Cador, O.; Ouahab, L. Tetrathiafulvalene-amido-2-pyridine-N-oxide as Efficient Charge-Transfer Antenna Ligand for the sensitization of YbIII Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes. Chem. Eur. J. 2010, 16, 11926–11941. [Google Scholar] [CrossRef] [PubMed]
- Kahn, O. Molecular Magnetism; VCH: Weinhem, Germany, 1993. [Google Scholar]
- Da Cunha, T.T.; Jung, J.; Boulon, M.-E.; Campo, G.; Pointillart, F.; Pereira, L.M.; Le Guennic, B.; Cador, O.; Bernot, K.; Pineider, F.; et al. Magnetic Poles Determinations and Robustness of Memory Effect upon Solubilization in a DyIII-Based Single Ion Magnet. J. Am. Chem. Soc. 2013, 135, 16332–16335. [Google Scholar] [CrossRef] [PubMed]
- Latendresse, P.T.; Bhuvanesh, S.N.; Nippe, M. Slow Magnetic Relaxation in a Lanthanide-[1]Metallocenophane Complex. J. Am. Chem. Soc. 2017, 139, 8058–8061. [Google Scholar] [CrossRef] [PubMed]
- Gatteschi, D.; Sessoli, R. Quantum Tunneling of Magnetization and Related Phenomena in Molecular Materials. Angew. Chem. Int. Ed. 2003, 42, 268–297. [Google Scholar] [CrossRef] [PubMed]
- Ishikawa, N.; Sugita, M.; Wernsdorfer, W. Quantum Tunneling of Magnetization in Lanthanide Single-Molecule Magnets: Bis(phthalocyaninato)terbium and Bis(phthalocyaninato)dysprosium Anions. Angew. Chem. Int. Ed. 2005, 44, 2931–2935. [Google Scholar] [CrossRef] [PubMed]
- Guo, Y.-N.; Xu, G.-F.; Wernsdorfer, W.; Ungur, L.; Guo, Y.; Tang, J.; Zhang, H.-J.; Chibotaru, L.F.; Powell, A.K. Strong axiality and ising exchange interaction suppress zero-field tunneling of magnetization of an asymmetric Dy2 single-molecule magnet. J. Am. Chem. Soc. 2011, 133, 11948–11951. [Google Scholar] [CrossRef] [PubMed]
- Ishikawa, N.; Sugita, M.; Wernsdorfer, W. Nuclear Spin Driven Quantum Tunneling of Magnetization in a New Lanthanide Single-Molecule Magnet: Bis(Phthalocyaninato)holmium Anion. J. Am. Chem. Soc. 2005, 127, 3650–3651. [Google Scholar] [CrossRef] [PubMed]
- Pointillart, F.; Bernot, K.; Golhen, S.; Le Guennic, B.; Guizouarn, T.; Ouahab, L.; Ouahab, L. Magnetic Memory in an Isotopically Enriched and Magnetically Isolated Mononuclear Dysprosium Complex. Angew. Chem. Int. Ed. 2015, 54, 1504–1507. [Google Scholar] [CrossRef] [PubMed]
- Ungur, L.; Chibotaru, L.F. Magnetic anisotropy in the excited states of low symmetry lanthanide complexes. Phys. Chem. Chem. Phys. 2011, 13, 20086–20090. [Google Scholar] [CrossRef] [PubMed]
- Cole, K.S.; Cole, R.H. Dispersion and absorption in dielectrics I. Alternating current characteristics. J. Chem. Phys. 1941, 9, 341–351. [Google Scholar] [CrossRef]
- Orbach, R. Spin-lattice relaxation in rare-earth salts. Proc. R. Soc. A 1961, 264, 458–484. [Google Scholar] [CrossRef]
- Orbach, R. On the theory of spin-lattice relaxation in paramagnetic salts. Proc. Phys. Soc. 1961, 77, 821–826. [Google Scholar] [CrossRef]
- Abragam, A.; Bleaney, B. Electron Paramagnetic Resonance of Transition Ions; Clarendon Press: Oxford, UK, 1970. [Google Scholar]
- Shrivastava, K.N. Theory of spin–lattice relaxation. Phys. Status Solidi 1983, 117, 437–458. [Google Scholar] [CrossRef]
- Scott, P.L.; Jeffries, C.D. Spin-lattice relaxation in some rare-earth salts at helium temperatures; observation of the phonon bottleneck. Phys. Rev. 1962, 127, 32–51. [Google Scholar] [CrossRef]
- Richardson, M.F.; Wagner, W.F.; Sands, D.E. Rare-earth trishexafluoroacetylacetonates and related compounds. J. Inorg. Nucl. Chem. 1968, 30, 1275–1289. [Google Scholar] [CrossRef]
- Sheldrick, G.L. SHELXT—Integrated space-group and crystal-structure determination. Acta Crystallogr. Sect. A 2015, 71, 3–8. [Google Scholar] [CrossRef] [PubMed]
- Sheldrick, G.M. Crystal structure refinement with SHELXL. Acta Crystallogr. Sect. C 2015, 71, 3–8. [Google Scholar]
Compound | {[Dy(hfac)3(L)]·2C6H14}n (1) |
---|---|
Formula | C63H73DyF18O10S4 |
M/g·mol−1 | 1622.95 |
Crystal system | Monoclinic |
Space group | P21/c (N°14) |
Cell parameters | a = 15.8351(14) Å b = 23.8650(20) Å c = 19.0098(19) Å |
Volume/Å3 | 7047.4(11) |
Z | 4 |
T/K | 150(2) |
2θ range/° | 5.97 ≤ 2θ ≤ 50.48 |
ρcalc/g cm−3 | 1.530 |
µ/mm−1 | 1.280 |
Number of reflections | 62,952 |
Independent reflections | 16,127 |
Rint | 0.0608 |
Fo2 > 2σ(Fo)2 | 12,302 |
Number of variables | 813 |
R1, wR2 | 0.0436, 0.1003 |
Compound | 1 |
---|---|
Dy1–O1 | 2.296(3) |
Dy1–O4 | 2.237(3) |
Dy1–O5 | 2.360(3) |
Dy1–O6 | 2.430(3) |
Dy1–O7 | 2.370(3) |
Dy1–O8 | 2.389(3) |
Dy1–O9 | 2.395(3) |
Dy1–O10 | 2.346(3) |
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Flores Gonzalez, J.; Cador, O.; Ouahab, L.; Norkov, S.; Kuropatov, V.; Pointillart, F. Field-Induced Dysprosium Single-Molecule Magnet Involving a Fused o-Semiquinone-Extended-Tetrathiafulvalene-o-Semiquinone Bridging Triad. Inorganics 2018, 6, 45. https://doi.org/10.3390/inorganics6020045
Flores Gonzalez J, Cador O, Ouahab L, Norkov S, Kuropatov V, Pointillart F. Field-Induced Dysprosium Single-Molecule Magnet Involving a Fused o-Semiquinone-Extended-Tetrathiafulvalene-o-Semiquinone Bridging Triad. Inorganics. 2018; 6(2):45. https://doi.org/10.3390/inorganics6020045
Chicago/Turabian StyleFlores Gonzalez, Jessica, Olivier Cador, Lahcène Ouahab, Sergey Norkov, Viacheslav Kuropatov, and Fabrice Pointillart. 2018. "Field-Induced Dysprosium Single-Molecule Magnet Involving a Fused o-Semiquinone-Extended-Tetrathiafulvalene-o-Semiquinone Bridging Triad" Inorganics 6, no. 2: 45. https://doi.org/10.3390/inorganics6020045