TY - JOUR
T1 - Magnetic behavior in metal-free radical thin films
AU - Junghoefer, Tobias
AU - Calzolari, Arrigo
AU - Baev, Ivan
AU - Glaser, Mathias
AU - Ciccullo, Francesca
AU - Giangrisostomi, Erika
AU - Ovsyannikov, Ruslan
AU - Kielgast, Fridtjof
AU - Nissen, Matz
AU - Schwarz, Julius
AU - Gallagher, Nolan M.
AU - Rajca, Andrzej
AU - Martins, Michael
AU - Casu, Maria Benedetta
N1 - Funding Information:
This paper is in the memory of Wilfried Wurth. He was a brilliant scientist open to new ideas and views. We are deeply saddened that he will not see the result of our work, because it was made possible thanks to Wilfried's unprejudiced scientific approach. He would have appeared as a co-author. The authors would like to thank Helmholtz-Zentrum Berlin (HZB) for providing beamtime at BESSY II (Berlin, Germany), and DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities at PETRA III, Tang Zahng, Moritz Hoesch, Kai Bagschik, Hilmar Adler, Elke Nadler, and Sergio Naselli for technical support. We also thank Eberhard Goering for the XAS normalization method. Financial support from HZB, DESY, and German Research Foundation (DFG) under the contract CA852/5-2 and CA852/11-1 is gratefully acknowledged. We thank the National Science Foundation (NSF), Chemistry Division, for support of this research under grant nos. CHE-1665256 (A.R.) and CHE-1955349 (A.R.). T.J. I.B. M.G. F.K. M.N. J.S. M.M. and M.B.C. took part in the beamtimes at PETRA III. M.G. F.C. E.G. R.O. and M.B.C. took part in the beamtimes at BESSY II. N.M.G. and A.R. designed and synthetized the radical. A.C. performed the calculations. M.B.C. conceived and supervised the project, interpreted the data, and wrote the manuscript together with A.C. All authors contributed to the discussion and commented on the manuscript. The authors declare no competing interests.
Funding Information:
The authors would like to thank Helmholtz-Zentrum Berlin (HZB) for providing beamtime at BESSY II (Berlin, Germany), and DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities at PETRA III, Tang Zahng, Moritz Hoesch, Kai Bagschik, Hilmar Adler, Elke Nadler, and Sergio Naselli for technical support. We also thank Eberhard Goering for the XAS normalization method. Financial support from HZB , DESY , and German Research Foundation (DFG) under the contract CA852/5-2 and CA852/11-1 is gratefully acknowledged. We thank the National Science Foundation (NSF), Chemistry Division, for support of this research under grant nos. CHE-1665256 (A.R.) and CHE-1955349 (A.R.).
Publisher Copyright:
© 2021 Elsevier Inc.
PY - 2022/3/10
Y1 - 2022/3/10
N2 - Magnetism in organic materials is very intriguing: the realization of long-range magnetic order in completely metal-free systems combines magnetic moments with useful properties of organic materials. An essential step for applications is the knowledge of the magnetic behavior that, so far, was investigated only in the proximity of light atoms to heavy metals, impurities, or vacancies, and not as an intrinsic property of thin films that are purely organic. Here, we unravel X-ray magnetic circular dichroism at the carbon and nitrogen K-edges in purely organic radical thin films. Our results show that, controlling the preparation, the magnetic behavior is different than in single crystals. Atomistic simulations indicate that the reason for this is the molecular arrangement in the films when compared with that in the single crystal. The tuning of the film magnetic properties by the molecular arrangement is an exciting perspective toward revealing new properties and applications.
AB - Magnetism in organic materials is very intriguing: the realization of long-range magnetic order in completely metal-free systems combines magnetic moments with useful properties of organic materials. An essential step for applications is the knowledge of the magnetic behavior that, so far, was investigated only in the proximity of light atoms to heavy metals, impurities, or vacancies, and not as an intrinsic property of thin films that are purely organic. Here, we unravel X-ray magnetic circular dichroism at the carbon and nitrogen K-edges in purely organic radical thin films. Our results show that, controlling the preparation, the magnetic behavior is different than in single crystals. Atomistic simulations indicate that the reason for this is the molecular arrangement in the films when compared with that in the single crystal. The tuning of the film magnetic properties by the molecular arrangement is an exciting perspective toward revealing new properties and applications.
KW - SDG12: Responsible consumption and production
KW - SDG9: Industry innovation and infrastructure
KW - X-ray absorption
KW - X-ray magnetic circular dichroism
KW - ab initio calculations
KW - low temperature
KW - magnetism
KW - organic radicals
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U2 - 10.1016/j.chempr.2021.11.021
DO - 10.1016/j.chempr.2021.11.021
M3 - Article
AN - SCOPUS:85122934421
VL - 8
SP - 801
EP - 814
JO - Chem
JF - Chem
SN - 2451-9294
IS - 3
ER -