A {CoIII2DyIII4} Single-Molecule Magnet with an Expanded Core Structure

Crystal Growth & Design, vol. 23, pp. 395–402

Abstract

The coordination cluster compound [Co III 2 Dy III 4 (OH) 2 (ib) 8 (bdea) 2 (NO 3 ) 4 (H 2 O) 2 ]·2MeCN ( 1 ) self-assembles in a high-yield reaction of cobalt(II) isobutyrate (ib) with Dy(NO 3 ) 3 ·6H 2 O and N -butyldiethanolamine (H 2 bdea) in air. The C i -symmetric {Co III 2 Dy III 4 } core fragment features two {CoDy 2 (μ 3 -OH)} triangles, joined by one of their Dy sites via μ-O and μ-carboxylate bridges. This results in a flat zigzag metal skeleton, in contrast to previously reported hexanuclear {Co 2 Ln 4 (μ 3 -OH) 2 } clusters, namely, exhibiting a more condensed combination of two {CoLn 2 (μ 3 -OH)} triangles that form a Dy 4 rhombus. According to ac susceptibility measurements, this rearrangement in 1 reduces quantum tunneling of the magnetization and hence pushes up the onset of pronounced out-of-phase signals at zero bias field to 14 K, a significant change vs the more condensed {Co 2 Dy 4 } structures. As intermolecular interactions between coordination clusters in the solid state are well-known to also influence SMM features, comparative Hirshfeld surface analyses are also presented.

Authors 6

1. Dumitru Stati

   Institute of Applied Physics

   Affiliation as printed

   Institute of Applied Physics, 2028 Chisinau, R. Moldova

2. Jan van Leusen Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry, RWTH Aachen University, 52074 Aachen, Germany

3. Naushad Ahmed

   Indian Institute of Technology Hyderabad

   Affiliation as printed

   Department of Chemistry, IIT Hyderabad, Kandi, Telangana 502285, India

4. Victor Kravtsov

   Institute of Applied Physics

   Affiliation as printed

   Institute of Applied Physics, 2028 Chisinau, R. Moldova

5. Paul Kögerler corresponding Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry, RWTH Aachen University, 52074 Aachen, Germany

6. Svetlana G. Baca corresponding

   Institute of Applied Physics

   Affiliation as printed

   Institute of Applied Physics, 2028 Chisinau, R. Moldova