Hexadecanuclear isobutyrate nanoclusters with a {Co II14Co III2} core†
a
Jan
van Leusen,
b
Victor Ch.
Kravtsov,
a
Karl
Krämer,
c
Shi-Xia
Liu,
c
Silvio
Decurtins,
c
Paul
Kögerler
b
and
Svetlana G.
Baca
*a
Abstract
Charge-neutral hexadecanuclear nanoclusters [Co16(OH)4(ib)20(thme)2(Hthme)2(H2O)6]·MeCN·4H2O (1) and [Co16(OH)4(ib)20(thmp)2(Hthmp)2(H2O)6]·MeCN·4H2O (2) have been prepared from the reaction of Co(II) isobutyrate (Co(ib)2) with 1,1,1-tris(hydroxymethyl)ethane (H3thme) or 1,1,1-tris(hydroxymethyl)propane (H3thmp) and comprehensively characterized. Single-crystal X-ray diffraction reveals that the common mixed-valent centrosymmetric {Co(II)14Co(III)2} core of 1 and 2 represents an unprecedented arrangement of two planar {Co7} disk-like fragments with a central Co(III) ion surrounded by six Co(II) ions connected by two additional Co(II) ions. The two {Co7} fragments are non-coplanar and lie in parallel planes separated by a distance of 2.772 Å, with two additional Co(II) centers between these planes. Hirshfeld surface (HS) analysis was used to gain additional insight into the interactions responsible for the packing of nanoclusters in the title compounds. Magnetic characterization of 1 revealed that the 14 Co(II) centers exhibit predominantly ferromagnetic exchange interactions, but some antiferromagnetic exchange pathways are also present.
- This article is part of the themed collection: Articles behind the 2024 journal covers
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