TY - JOUR
AU - Boukhvalov, D.
AU - Dobrovitski, V.
AU - Kögerler, P.
AU - Al-Saqer, M.
AU - Katsnelson, M.
AU - Lichtenstein, A.
AU - Harmon, B.
TI - Effect of ligand substitution on the exchange interactions in {Mn12}-type single-molecule magnets
JO - Inorganic chemistry
VL - 49
SN - 0020-1669
CY - Washington, DC
PB - American Chemical Society
M1 - PreJuSER-13146
SP - 10902
PY - 2010
N1 - 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.
AB - 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.
KW - J (WoSType)
LB - PUB:(DE-HGF)16
C6 - pmid:21043473
UR - <Go to ISI:>//WOS:000284518800022
DO - DOI:10.1021/ic101229p
UR - https://juser.fz-juelich.de/record/13146
ER -