Publication
Title
Changes in aromaticity of spin-crossover complexes : a signature for non-innocent ligands
Author
Abstract
The influence of the spin state of the metal centre in spin crossover compounds on the aromaticity of the ligands has been investigated for iron(ii)tris-bipyridine (Fe(bpy)32+), and Fe(ii)(formazanate)2 (as a truncated model and the full phenyl substituted compound). It was found that the aromaticity of the bipyridine ligands is unaffected by changing the spin state of the central iron atom, but that of the formazanate ligands is reduced upon transition to the high-spin state. This change in aromaticity is rationalized using the symmetry selection rules for aromaticity in terms of virtual excitations from occupied to empty orbitals. A further consequence of this loss in aromaticity is a shift to higher energy in the ring vibrations of the formazanate compounds that can be observed in either its IR or Raman spectrum; this prediction has been confirmed here. This change in aromaticity as a consequence of change in spin state can be regarded as an indication for non-innocent ligands. Aromaticity of non-innocent ligands is affected when the spin state changes.
Language
English
Source (journal)
Dalton Transactions : an international journal of inorganic chemistry / Royal Society of Chemistry [London] - Cambridge, 2003, currens
Publication
Cambridge : Royal soc chemistry , 2024
ISSN
1477-9226 [print]
1477-9234 [online]
DOI
10.1039/D3DT03404F
Volume/pages
(2024) , 8 p.
ISI
001142710300001
Pubmed ID
38226858
Full text (Publisher's DOI)
Full text (open access)
UAntwerpen
Faculty/Department
Research group
Publication type
Subject
Affiliation
Publications with a UAntwerp address
External links
Web of Science
Record
Identifier
Creation 01.02.2024
Last edited 06.02.2024
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