The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]
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Abstract
The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca)2] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χmT are in general agreement for [Co(dpzca)2], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca)2] at 15 K.
Acknowledgments
This research was supported by the National Science Foundation through the Nebraska MRSEC (DMR-1420645) and through the Division of Chemistry and Division of Materials Research (NSF-1565692). Partial financial support of the Nebraska Center for Energy Sciences Research (cycle 11) is also gratefully acknowledged. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
References
1. R. G. Miller, S. Narayanaswamy, J. L. Tallon, S. Brooker, New J. Chem. 38 (2014) 1932.10.1039/c3nj01451gSearch in Google Scholar
2. M. G. Cowan, R. G. Miller, S. Brooker, Dalton Trans. 44 (2015) 2880.10.1039/C4DT03407DSearch in Google Scholar
3. M. G. Cowan, J. Olguín, S. Narayanaswamy, J. L. Tallon, S. Brooker, J. Am. Chem. Soc. 134 (2012) 2892.10.1021/ja208429uSearch in Google Scholar PubMed
4. R. G. Miller, S. Narayanaswamy, S. M. Clark, P. Dera, G. B. Jameson, J. L. Tallon, S. Brooker, Dalton Trans. 44 (2015) 20843.10.1039/C5DT03795FSearch in Google Scholar PubMed
5. X. Zhang, S. Mu, G. Chastanet, N. Daro, T. Palamarciuc, P. Rosa, J.-F. Létard, J. Liu, G. E. Sterbinsky, D. A. Arena, C. Etrillard, B. Kundys, B. Doudin, P. A. Dowben, J. Phys. Chem. C 119 (2015) 16293.10.1021/acs.jpcc.5b02220Search in Google Scholar
6. P. Nachimuthu, J. H. Underwood, C. D. Kemp, E. M. Gullikson, D. W. Lindle, D. K. Shuh, R. C. C. Perera, in: AIP Conf. Proc., AIP Publishing, (2004), P. 454.10.1063/1.1757832Search in Google Scholar
7. P. E. Blöchl, Phys. Rev. B 50 (1994) 17953.10.1103/PhysRevB.50.17953Search in Google Scholar PubMed
8. G. Kresse, J. Hafner, Phys. Rev. B 48 (1993) 13115.10.1103/PhysRevB.48.13115Search in Google Scholar PubMed
9. G. Kresse, J. Furthmüller, Phys. Rev. B 54 (1996) 11169.10.1103/PhysRevB.54.11169Search in Google Scholar PubMed
10. A. I. Liechtenstein, V. I. Anisimov, J. Zaanen, Phys. Rev. B 52 (1995) R5467.10.1103/PhysRevB.52.R5467Search in Google Scholar
11. J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865.10.1103/PhysRevLett.77.3865Search in Google Scholar PubMed
12. J. Chen, A. J. Millis, C. A. Marianetti, Phys. Rev. B 91 (2015) 241111.10.1103/PhysRevB.91.241111Search in Google Scholar
13. X. Zhang, T. Palamarciuc, J.-F. Létard, P. Rosa, E. V. Lozada, F. Torres, L. G. Rosa, B. Doudin, P. A. Dowben, Chem. Commun. 50 (2014) 2255.10.1039/c3cc46892eSearch in Google Scholar PubMed
14. J.-F. Létard, P. Guionneau, L. Goux-Capes, Towards Spin Crossover Applications, in: P. Gütlich, H. A. Goodwin (Eds.): Spin Crossover Transit. Met. Compd. III, Springer, Berlin Heidelberg (2004), P. 221–249.10.1007/b95429Search in Google Scholar
15. P. Gütlich, H. A. Goodwin, in: P. Gütlich, H. A. Goodwin (Eds.): Spin Crossover Transit. Met. Compd. I, Springer Berlin Heidelberg (2004), P. 1–47.10.1007/b96439Search in Google Scholar
16. O. Sato, J. Tao, Y.-Z. Zhang, Angew. Chem. Int. Ed. 46 (2007) 2152.10.1002/anie.200602205Search in Google Scholar PubMed
17. J. A. Real, A. B. Gaspar, M. C. Muñoz, Dalton Trans. (2005) 2062.10.1039/b501491cSearch in Google Scholar PubMed
18. J.-J. Lee, H. Sheu, C.-R. Lee, J.-M. Chen, J.-F. Lee, C.-C. Wang, C.-H. Huang, Y. Wang, J. Am. Chem. Soc. 122 (2000) 5742.10.1021/ja9943290Search in Google Scholar
19. B. Warner, J. C. Oberg, T. G. Gill, F. El Hallak, C. F. Hirjibehedin, M. Serri, S. Heutz, M.-A. Arrio, P. Sainctavit, M. Mannini, G. Poneti, R. Sessoli, P. Rosa, J. Phys. Chem. Lett. 4 (2013) 1546.10.1021/jz4005619Search in Google Scholar PubMed
20. T. G. Gopakumar, M. Bernien, H. Naggert, F. Matino, C. F. Hermanns, A. Bannwarth, S. Mühlenberend, A. Krüger, D. Krüger, F. Nickel, W. Walter, R. Berndt, W. Kuch, F. Tuczek, Chem. – Eur. J. 19 (2013) 15702.10.1002/chem.201302241Search in Google Scholar PubMed
21. J.-F. Létard, G. Chastanet, P. Guionneau, C. Desplanches, Optimizing the Stability of Trapped Metastable Spin States, in: L. a Halcrow (Ed.): Spin-Crossover Mater., John Wiley & Sons Ltd, New York (2013), P. 475–506.10.1002/9781118519301.ch19Search in Google Scholar
22. M. Marchivie, P. Guionneau, J. A. K. Howard, G. Chastanet, J.-F. Létard, A. E. Goeta, D. Chasseau, J. Am. Chem. Soc. 124 (2002) 194.10.1021/ja016980kSearch in Google Scholar
23. L. Capes, J.-F. Létard, O. Kahn, Chem. – Eur. J. 6 (2000) 2246.10.1002/1521-3765(20000616)6:12<2246::AID-CHEM2246>3.0.CO;2-XSearch in Google Scholar
24. N. Moliner, L. Salmon, L. Capes, M. C. Muñoz, J.-F. Létard, A. Bousseksou, J.-P. Tuchagues, J. J. McGarvey, A. C. Dennis, M. Castro, R. Burriel, J. A. Real, J. Phys. Chem. B 106 (2002) 4276.10.1021/jp013872bSearch in Google Scholar
25. W. Zhang, R. Alonso-Mori, U. Bergmann, C. Bressler, M. Chollet, A. Galler, W. Gawelda, R. G. Hadt, R. W. Hartsock, T. Kroll, K. S. Kjær, K. Kubiček, H. T. Lemke, H. W. Liang, D. A. Meyer, M. M. Nielsen, C. Purser, J. S. Robinson, E. I. Solomon, Z. Sun, D. Sokaras, T. B. van Driel, G. Vankó, T.-C. Weng, D. Zhu, K. J. Gaffney, Nature 509 (2014) 345.10.1038/nature13252Search in Google Scholar
26. C. Creutz, M. Chou, T. L. Netzel, M. Okumura, N. Sutin, J. Am. Chem. Soc. 102 (1980) 1309.10.1021/ja00524a014Search in Google Scholar
27. N. Huse, H. Cho, K. Hong, L. Jamula, F. M. F. de Groot, T. K. Kim, J. K. McCusker, R. W. Schoenlein, J. Phys. Chem. Lett. 2 (2011) 880.10.1021/jz200168mSearch in Google Scholar
28. H. T. Lemke, C. Bressler, L. X. Chen, D. M. Fritz, K. J. Gaffney, A. Galler, W. Gawelda, K. Haldrup, R. W. Hartsock, H. Ihee, J. Kim, K. H. Kim, J. H. Lee, M. M. Nielsen, A. B. Stickrath, W. Zhang, D. Zhu, M. Cammarata, J. Phys. Chem. A 117 (2013) 735.10.1021/jp312559hSearch in Google Scholar
29. W. Zhang, K. S. Kjær, R. Alonso-Mori, U. Bergmann, M. Chollet, L. A. Fredin, R. G. Hadt, R. W. Hartsock, T. Harlang, T. Kroll, K. Kubiček, H. T. Lemke, H. W. Liang, Y. Liu, M. M. Nielsen, P. Persson, J. S. Robinson, E. I. Solomon, Z. Sun, D. Sokaras, T. B. van Driel, T.-C. Weng, D. Zhu, K. Wärnmark, V. Sundström, K. J. Gaffney, Chem. Sci. 8 (2016) 515.10.1039/C6SC03070JSearch in Google Scholar
30. T. Tezgerevska, K. G. Alley, C. Boskovic, Coord. Chem. Rev. 268 (2014) 23.10.1016/j.ccr.2014.01.014Search in Google Scholar
31. J. Tao, H. Maruyama, O. Sato, J. Am. Chem. Soc. 128 (2006) 1790.10.1021/ja057488uSearch in Google Scholar
©2018 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Frontmatter
- The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]
- Thermal Degradation of Complexes Derived from Cu (II) Groundnut (Arachis hypogaea) and Sesame (Sesamum indicum) Soaps
- Effect of Mesoporous Diatomite Particles on the Kinetics of SR&NI ATRP of Styrene and Butyl Acrylate
- Removal of Hexavalent Chromium by Adsorption on Microwave Assisted Activated Carbon Prepared from Stems of Leucas Aspera
- Removal of Acid Yellow 17 Dye by Fenton Oxidation Process
- The Efficient Removal of Heavy Metal Ions from Industry Effluents Using Waste Biomass as Low-Cost Adsorbent: Thermodynamic and Kinetic Models
- Degradation of Acetaminophen in Aqueous Media by H2O2 Assisted Gamma Irradiation Process
- M(Al,Ni)-TiO2-Based Photoanode for Photoelectrochemical Solar Cells
- Quantum Mechanical Study of γ-Fe2O3 Nanoparticle as a Nanocarrier for Anticancer Drug Delivery
- Corrigendum
- Corrigendum to: Green Synthesis of CoFe2O4 and Investigation of its Catalytic Efficiency for Degradation of Dyes in Aqueous Medium
Articles in the same Issue
- Frontmatter
- The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]
- Thermal Degradation of Complexes Derived from Cu (II) Groundnut (Arachis hypogaea) and Sesame (Sesamum indicum) Soaps
- Effect of Mesoporous Diatomite Particles on the Kinetics of SR&NI ATRP of Styrene and Butyl Acrylate
- Removal of Hexavalent Chromium by Adsorption on Microwave Assisted Activated Carbon Prepared from Stems of Leucas Aspera
- Removal of Acid Yellow 17 Dye by Fenton Oxidation Process
- The Efficient Removal of Heavy Metal Ions from Industry Effluents Using Waste Biomass as Low-Cost Adsorbent: Thermodynamic and Kinetic Models
- Degradation of Acetaminophen in Aqueous Media by H2O2 Assisted Gamma Irradiation Process
- M(Al,Ni)-TiO2-Based Photoanode for Photoelectrochemical Solar Cells
- Quantum Mechanical Study of γ-Fe2O3 Nanoparticle as a Nanocarrier for Anticancer Drug Delivery
- Corrigendum
- Corrigendum to: Green Synthesis of CoFe2O4 and Investigation of its Catalytic Efficiency for Degradation of Dyes in Aqueous Medium
