2016
DOI: 10.1002/chem.201602444
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Electronic Modulation of the SOMO–HOMO Energy Gap in Iron(III) Complexes towards Unimolecular Current Rectification

Abstract: Amphiphilic five-coordinate iron(III) complexes with {N2 O2 Cl} and {N2 O3 } coordination spheres are studied to elucidate the roles of electronic structure on the mechanisms for current rectification. The presence of an apical chlorido or phenolato ligand plays a crucial role, and the [Fe(III) {N2 O2 Cl}] species supports an asymmetric mechanism while its [Fe(III) {N2 O3 }] counterpart seems to allow for unimolecular mechanism. The effects of electron-donating and electron-withdrawing substituents in the liga… Show more

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Cited by 15 publications
(6 citation statements)
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“…This is summarized in Figure 9d−f. Both of these proposed electron transport pathways differ from that described for 3d 5 iron- based species 3 10 and other Fe III species with similar ligand environments 57,58 in which the metal-centered SOMO is a linear combination of d xz + d yz located ca. 1.0 eV above the Fermi level (Figure 7).…”
Section: Synthesis and Characterizationscontrasting
confidence: 61%
“…This is summarized in Figure 9d−f. Both of these proposed electron transport pathways differ from that described for 3d 5 iron- based species 3 10 and other Fe III species with similar ligand environments 57,58 in which the metal-centered SOMO is a linear combination of d xz + d yz located ca. 1.0 eV above the Fermi level (Figure 7).…”
Section: Synthesis and Characterizationscontrasting
confidence: 61%
“…1,51 Complexes C1-C3 all display a distorted trigonal bipyramidal geometry, in contrast to the square pyramidal geometries often observed with Fe(III) salen complexes. [52][53][54][55] The flexible coordination modes available when using phenoxyimine ligands may present an advantage over the well-established salen analogues. These findings suggest that phenoxyimine ligand supported metal complexes have significant potential for a broad scope of CO 2 /epoxide coupling reactions.…”
Section: Papermentioning
confidence: 99%
“…These energies are given in eV and are similar to the respective LUMO and HOMO energies of the metallosurfactants. 90,91 However, because 3d metals display electronic configurations with unpaired electrons, reduction usually entails population of the lowest singly occupied MO, and the orbital in question is indeed a metal-based SOMO. On the other hand, the oxidation process is ligand based and therefore associated with an available HOMO.…”
Section: X-ray Photoelectron Spectroscopy (Xps)mentioning
confidence: 99%