Document type
ArticleVersion
Accepted versionPublication date
All rights reserved
Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/154698
Electronic and steric control of the spin-crossover behavior in [(Cp-R)(2)Mn] manganocenes
Journal Title
Director/Tutor
Journal ISSN
Volume Title
Related resource
Abstract
A computational study of the spin-crossover behavior in the family [(Cp-R)(2)Mn] (R = Me, Pr-i, Bu-t) is presented. Using the OPBE functional, the different electronic and steric effects over the metal's ligand field are studied, and trends in the spin-crossover-temperature (T-1/2) behavior are presented in terms of the cyclopentadienyl (Cp) ligand functionalization. Our calculations outlined a delicate balance between both electronic and steric effects. While an increase in the number of electron donating groups increases the spin-crossover temperature (T-1/2) to the point that the transition is suppressed and only the low-spin state is observed, steric effects play an opposite role, increasing the distance between the Cp rings, which in turns shifts T-1/2 to lower values, eventually stabilizing the high-spin state. Both effects can be rationalized by exploring the electronic structure of such systems in terms of the relevant d-based molecular orbitals.
Citation
Citation
CIRERA FERNÁNDEZ, Jordi and RUIZ SABÍN, Eliseo. Electronic and steric control of the spin-crossover behavior in [(Cp-R)(2)Mn] manganocenes. Inorganic Chemistry. 2018. Vol. 57, num. 2, pags. 702-709. ISSN 0020-1669. [consulted: 12 of August of 2026]. Available at: https://hdl.handle.net/2445/154698