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Mn 12 ‐Acetate Complexes Studied as Single Molecules
Author(s) -
Tombers Matthias,
Meyer Jennifer,
Meyer Jonathan,
Lawicki Arkadiusz,
ZamudioBayer Vicente,
Hirsch Konstantin,
Lau J. Tobias,
Issendorff Bernd,
Terasaki Akira,
Schlathölter Thomas A.,
Hoekstra Ronnie A.,
Schmidt Sebastian,
Powell Annie K.,
Kessler Eva,
Prosenc Marc H.,
Wüllen Christoph,
NiednerSchatteburg Gereon
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202102592
Subject(s) - crystallography , molecule , anisotropy , single molecule magnet , materials science , magnetic anisotropy , chemistry , magnetization , magnetic field , physics , organic chemistry , quantum mechanics
The phenomenon of single molecule magnet (SMM) behavior of mixed valent Mn 12 coordination clusters of general formula [Mn III 8 Mn IV 4 O 12 (RCOO) 16 (H 2 O) 4 ] had been exemplified by bulk samples of the archetypal [Mn III 8 Mn IV 4 O 12 (CH 3 COO) 16 (H 2 O) 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 12 O 12 (CH 3 COO) 15 (CH 3 CN)] + (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 12 O 12 (CH 3 COO) 15 (CH 3 CN)] + (1) , [Mn 12 O 12 (CH 3 COO) 16 ] (2) , [Mn 12 O 12 (CH 3 COO) 16 (H 2 O) 4 ] (3) , and the complex in bulk geometry [Mn III 8 Mn IV 4 O 12 (CH 3 COO) 16 (H 2 O) 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.