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Slow Magnetic Relaxation of a 12-Metallacrown-4 Complex with a Manganese(III)-Copper(II) Heterometallic Ring Motif.

Authors :
Lewis AJ
Garlatti E
Cugini F
Solzi M
Zeller M
Carretta S
Zaleski CM
Source :
Inorganic chemistry [Inorg Chem] 2020 Sep 08; Vol. 59 (17), pp. 11894-11900. Date of Electronic Publication: 2020 Aug 19.
Publication Year :
2020

Abstract

The heterobimetallic metallacrown (MC), (TMA) <subscript>2</subscript> {Mn(OAc) <subscript>2</subscript> [12-MC <subscript>Mn(III)Cu(II)N(shi)</subscript> -4](CH <subscript>3</subscript> OH)}·2.90CH <subscript>3</subscript> OH, 1 , where TMA <superscript>+</superscript> is tetramethylammonium, <superscript>-</superscript> OAc is acetate, and shi <superscript>3-</superscript> is salicylhydroximate, consists of a Mn <superscript>II</superscript> ion captured in the central cavity and alternating unambiguous and ordered manganese(III) and copper(II) sites about the MC ring, a first for the archetypal MC structure design. DC-magnetometry characterization and subsequent simulation with the Spin Hamiltonian H = - J <subscript>1</subscript> ( s <subscript>1</subscript> + s <subscript>3</subscript> )· s <subscript>5</subscript> - J <subscript>2</subscript> ( s <subscript>2</subscript> + s <subscript>4</subscript> )· s <subscript>5</subscript> - J <subscript>3</subscript> Σ <subscript>i=1</subscript> <superscript>4</superscript> s <subscript> i </subscript> · s <subscript> i +1</subscript> + d ( s <subscript> z ,1</subscript> <superscript>2</superscript> + s <subscript> z ,3</subscript> <superscript>2</superscript> ) + μ <subscript>B</subscript> Σ <subscript>j=1</subscript> <superscript>5</superscript> g <subscript> j </subscript> s <subscript>j</subscript> · B indicates an S = 5/2 ground state and a sizable axial zero-field splitting on Mn <superscript>III</superscript> . AC-susceptibility measurements reveal that 1 displays slow magnetization relaxation akin to single-molecule magnet (SMM) behavior.

Details

Language :
English
ISSN :
1520-510X
Volume :
59
Issue :
17
Database :
MEDLINE
Journal :
Inorganic chemistry
Publication Type :
Academic Journal
Accession number :
32812746
Full Text :
https://doi.org/10.1021/acs.inorgchem.0c01410