Effect of Ligand Substitution on the Exchange Interactions in {Mn-12}-Type Single-Molecule Magnets

TitleEffect of Ligand Substitution on the Exchange Interactions in {Mn-12}-Type Single-Molecule Magnets
Publication TypeJournal Article
Year of Publication2010
AuthorsBoukhvalov DW, Dobrovitski VV, Kogerler P, Al-Saqer M, Katsnelson MI, Lichtenstein AI, Harmon BN
Journal TitleInorganic Chemistry
Volume49
Pages10902-10906
Date Published12/06
ISBN Number0020-1669
Accession NumberISI:000284518800022
Keywordscomplexes, FE-8, HIGH-SPIN MOLECULES, magnetization, mn-12, NANOMAGNETS, relaxation, symmetry
Abstract

We investigate how ligand substitution affects the intramolecular spin exchange interactions, studying a prototypical family of single-molecule magnets comprising dodecanuclear cluster molecules [(Mn8Mn4O12)-Mn-III-O-IV(COOR)(16)]. We identify a simple scheme based on accumulated Pauling electronegativity numbers (AEN) of the carboxylate ligand groups (R). The redistribution of the electron density, controlled by the AEN of a ligand, changes the degree of hybridization between 3d electrons of manganese and 2p electrons of oxygen atoms, thus changing the exchange interactions. This scheme, despite its conceptual simplicity, provides a strong correlation with the exchange energies associated with carboxylate bridges and is confirmed by the electronic structure calculations taking into account the Coulomb correlations in magnetic molecules.

URL<Go to ISI>://000284518800022
DOI10.1021/Ic101229p
Alternate JournalInorg Chem