TY - JOUR
T1 - Mn12-acetate complexes studied as single molecules
AU - Tombers, Matthias
AU - Meyer, Jennifer
AU - Meyer, Jonathan
AU - Lawicki, Arkadiucz
AU - Zamudio-Bayer, Vicente
AU - Hirsch, Konstantin
AU - Lau, J. Tobias
AU - von Issendorff, Bernd
AU - Terasaki, Akira
AU - Schlathölter, Thomas
AU - Hoekstra, Ronnie
AU - Schmidt, Sebastian
AU - Powell, Annie K.
AU - Kessler, Eva
AU - Prosenc, Marc H.
AU - van Wüllen, Christoph
AU - Niedner-Schatteburg, Gereon
N1 - Funding Information:
This work was supported through the DFG funded transregional collaborative research center SFB TRR 88 ?3MET.de? and the BMBF grant BMBF-05K13Vf2. We gratefully acknowledge the financial support and allocation of X-ray beam time at the UE52 ? PGM beamline from HZB at the BESSY II synchrotron radiation facility. We thank the Toyota Technological Institute for providing the superconducting magnet for the conducted experiments. We thank R. Sessoli for providing the bulk phase data shown in Figures 1b and 2, and we thank Joachim Hewer for valuable discussions. Finally, we want to thank the reviewers for valuable comments. Open Access funding enabled and organized by Projekt DEAL.
Funding Information:
This work was supported through the DFG funded transregional collaborative research center SFB TRR 88 “3MET.de” and the BMBF grant BMBF‐05K13Vf2. We gratefully acknowledge the financial support and allocation of X‐ray beam time at the UE52 – PGM beamline from HZB at the BESSY II synchrotron radiation facility. We thank the Toyota Technological Institute for providing the superconducting magnet for the conducted experiments. We thank R. Sessoli for providing the bulk phase data shown in Figures 1 b and 2, and we thank Joachim Hewer for valuable discussions. Finally, we want to thank the reviewers for valuable comments. Open Access funding enabled and organized by Projekt DEAL.
Publisher Copyright:
© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH
PY - 2022/1/10
Y1 - 2022/1/10
N2 - The phenomenon of single molecule magnet (SMM) behavior of mixed valent Mn
12 coordination clusters of general formula [Mn
III
8Mn
IV
4O
12(RCOO)
16(H
2O)
4] had been exemplified by bulk samples of the archetypal [Mn
III
8Mn
IV
4O
12(CH
3COO)
16(H
2O)
4] (4) molecule, and the molecular origin of the observed magnetic behavior has found support from extensive studies on the Mn
12 system within crystalline material or on molecules attached to a variety of surfaces. Here we report the magnetic signature of the isolated cationic species [Mn
12O
12(CH
3COO)
15(CH
3CN)]
+ (1) by gas phase X-ray Magnetic Circular Dichroism (XMCD) spectroscopy, and we find it closely resembling that of the corresponding bulk samples. Furthermore, we report broken symmetry DFT calculations of spin densities and single ion tensors of the isolated, optimized complexes [Mn
12O
12(CH
3COO)
15(CH
3CN)]
+ (1), [Mn
12O
12(CH
3COO)
16] (2), [Mn
12O
12(CH
3COO)
16(H
2O)
4] (3), and the complex in bulk geometry [Mn
III
8Mn
IV
4O
12(CH
3COO)
16(H
2O)
4] (5). The found magnetic fingerprints – experiment and theory alike – are of a remarkable robustness: The Mn
IV
4 core bears almost no magnetic anisotropy while the surrounding Mn
III
8 ring is highly anisotropic. These signatures are truly intrinsic properties of the Mn
12 core scaffold within all of these complexes and largely void of the environment. This likely holds irrespective of bulk packing effects.
AB - The phenomenon of single molecule magnet (SMM) behavior of mixed valent Mn
12 coordination clusters of general formula [Mn
III
8Mn
IV
4O
12(RCOO)
16(H
2O)
4] had been exemplified by bulk samples of the archetypal [Mn
III
8Mn
IV
4O
12(CH
3COO)
16(H
2O)
4] (4) molecule, and the molecular origin of the observed magnetic behavior has found support from extensive studies on the Mn
12 system within crystalline material or on molecules attached to a variety of surfaces. Here we report the magnetic signature of the isolated cationic species [Mn
12O
12(CH
3COO)
15(CH
3CN)]
+ (1) by gas phase X-ray Magnetic Circular Dichroism (XMCD) spectroscopy, and we find it closely resembling that of the corresponding bulk samples. Furthermore, we report broken symmetry DFT calculations of spin densities and single ion tensors of the isolated, optimized complexes [Mn
12O
12(CH
3COO)
15(CH
3CN)]
+ (1), [Mn
12O
12(CH
3COO)
16] (2), [Mn
12O
12(CH
3COO)
16(H
2O)
4] (3), and the complex in bulk geometry [Mn
III
8Mn
IV
4O
12(CH
3COO)
16(H
2O)
4] (5). The found magnetic fingerprints – experiment and theory alike – are of a remarkable robustness: The Mn
IV
4 core bears almost no magnetic anisotropy while the surrounding Mn
III
8 ring is highly anisotropic. These signatures are truly intrinsic properties of the Mn
12 core scaffold within all of these complexes and largely void of the environment. This likely holds irrespective of bulk packing effects.
KW - single molecule magnets
KW - XMCD spectroscopy
KW - broken symmetry DFT modelling
KW - gaseous ions
KW - single ion magnetic anisotropy tensors
U2 - 10.1002/chem.202102592
DO - 10.1002/chem.202102592
M3 - Article
SN - 0947-6539
VL - 28
JO - Chemistry
JF - Chemistry
IS - 2
M1 - e202102592
ER -