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Towards Iron(II) Complexes with Octahedral Geometry: Synthesis, Structure and Photophysical Properties
- Source :
- Molecules, Molecules, MDPI, 2020, 25 (24), pp.5991. ⟨10.3390/molecules25245991⟩, Volume 25, Issue 24, Molecules, Vol 25, Iss 5991, p 5991 (2020), Molecules, 2020, 25 (24), pp.5991. ⟨10.3390/molecules25245991⟩
- Publication Year :
- 2020
- Publisher :
- HAL CCSD, 2020.
-
Abstract
- The control of ligand-field splitting in iron (II) complexes is critical to slow down the metal-to-ligand charge transfer (MLCT)-excited states deactivation pathways. The gap between the metal-centered states is maximal when the coordination sphere of the complex approaches an ideal octahedral geometry. Two new iron(II) complexes (C1 and C2), prepared from pyridylNHC and pyridylquinoline type ligands, respectively, have a near-perfect octahedral coordination of the metal. The photophysics of the complexes have been further investigated by means of ultrafast spectroscopy and TD-DFT modeling. For C1, it is shown that&mdash<br />despite the geometrical improvement&mdash<br />the excited state deactivation is faster than for the parent pseudo-octahedral C0 complex. This unexpected result is due to the increased ligand flexibility in C1 that lowers the energetic barrier for the relaxation of 3MLCT into the 3MC state. For C2, the effect of the increased ligand field is not strong enough to close the prominent deactivation channel into the metal-centered quintet state, as for other Fe-polypyridine complexes.
- Subjects :
- [CHIM.INOR] Chemical Sciences/Inorganic chemistry
Ligand field theory
Coordination sphere
Materials science
Iron
Pharmaceutical Science
excited states dynamics
[CHIM.INOR]Chemical Sciences/Inorganic chemistry
Crystallography, X-Ray
Ligands
010402 general chemistry
01 natural sciences
Article
time-resolved spectroscopy
Analytical Chemistry
lcsh:QD241-441
Metal
X-Ray Diffraction
lcsh:Organic chemistry
Drug Discovery
Octahedral molecular geometry
[CHIM.CRIS]Chemical Sciences/Cristallography
iron (II) complexes
[CHIM.COOR]Chemical Sciences/Coordination chemistry
Ferrous Compounds
[CHIM.CRIS] Chemical Sciences/Cristallography
Physical and Theoretical Chemistry
octahedral geometry
density functional theory
ComputingMilieux_MISCELLANEOUS
Molecular Structure
010405 organic chemistry
Ligand
Organic Chemistry
[CHIM.COOR] Chemical Sciences/Coordination chemistry
0104 chemical sciences
3. Good health
Crystallography
Octahedron
[CHIM.OTHE] Chemical Sciences/Other
Chemistry (miscellaneous)
Excited state
visual_art
visual_art.visual_art_medium
Thermodynamics
Molecular Medicine
Density functional theory
[CHIM.OTHE]Chemical Sciences/Other
Subjects
Details
- Language :
- English
- ISSN :
- 14203049
- Database :
- OpenAIRE
- Journal :
- Molecules, Molecules, MDPI, 2020, 25 (24), pp.5991. ⟨10.3390/molecules25245991⟩, Volume 25, Issue 24, Molecules, Vol 25, Iss 5991, p 5991 (2020), Molecules, 2020, 25 (24), pp.5991. ⟨10.3390/molecules25245991⟩
- Accession number :
- edsair.doi.dedup.....e4cc1b9ba5abd2dfcaeb567b6ec5eb9e