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The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK
Academic Editor: Martin T. Lemaire
Crystals 2016, 6(5), 58; https://doi.org/10.3390/cryst6050058
Received: 22 April 2016 / Revised: 11 May 2016 / Accepted: 13 May 2016 / Published: 18 May 2016
(This article belongs to the Special Issue High Spin Molecules)
The relationship between chemical structure and spin state in a transition metal complex has an important bearing on mechanistic bioinorganic chemistry, catalysis by base metals, and the design of spin crossover materials. The latter provide an ideal testbed for this question, since small changes in spin state energetics can be easily detected from shifts in the spin crossover equilibrium temperature. Published structure-function relationships relating ligand design and spin state from the spin crossover literature give varied results. A sterically crowded ligand sphere favors the expanded metal–ligand bonds associated with the high-spin state. However, steric clashes at the molecular periphery can stabilize either the high-spin or the low-spin state in a predictable way, depending on their effect on ligand conformation. In the absence of steric influences, the picture is less clear since electron-withdrawing ligand substituents are reported to favor the low-spin or the high-spin state in different series of compounds. A recent study has shed light on this conundrum, showing that the electronic influence of a substituent on a coordinated metal ion depends on its position on the ligand framework. Finally, hydrogen bonding to complexes containing peripheral N‒H groups consistently stabilizes the low-spin state, where this has been quantified. View Full-Text
Keywords: transition metals; spin state; spin crossover; structure–function relationships; magnetostructural correlations; magnetic measurements transition metals; spin state; spin crossover; structure–function relationships; magnetostructural correlations; magnetic measurements
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Halcrow, M.A. The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes. Crystals 2016, 6, 58.

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