%0 Journal Article
%A Boukhvalov, D.
%A Dobrovitski, V.
%A Kögerler, P.
%A Al-Saqer, M.
%A Katsnelson, M.
%A Lichtenstein, A.
%A Harmon, B.
%T Effect of ligand substitution on the exchange interactions in {Mn12}-type single-molecule magnets
%J Inorganic chemistry
%V 49
%@ 0020-1669
%C Washington, DC
%I American Chemical Society
%M PreJuSER-13146
%P 10902
%D 2010
%Z The work is financially supported by Stichting voor Fundamenteel Onderzoek der Materie (FOM), The Netherlands. Work at the Ames Laboratory was supported by the Department of Energy<SUP>-</SUP>Basic Energy Sciences under Contract No. DE-AC02-07CH11358.
%X We investigate how ligand substitution affects the intramolecular spin exchange interactions, studying a prototypical family of single-molecule magnets comprising dodecanuclear cluster molecules [Mn(III)(8)Mn(IV)(4)O(12)(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.
%K J (WoSType)
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:21043473
%U <Go to ISI:>//WOS:000284518800022
%R 10.1021/ic101229p
%U https://juser.fz-juelich.de/record/13146