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Electronic properties of ferrocenyl-terpyridine coordination complexes: An electrochemical and X-ray photoelectron spectroscopic approach.
- Source :
-
Inorganica Chimica Acta . Oct2018, Vol. 482, p514-521. 8p. - Publication Year :
- 2018
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Abstract
- Graphical abstract The electrochemical behavior of the Fc/Fc+ of ferrocenyl-terpyridine coordination metal complexes is related to the charge transfer and binding energy of the Fe 2p photoelectron lines as measured by XPS, giving insight into the electronic properties of the complexes. Highlights • Preparation of coordinated ferrocenyl-terpyridine complexes. • Electrochemical study of the coordinated ferrocenyl-terpyridine complexes. • X-ray photoelectron spectroscopy of ferrocenyl-terpyridine coordination complexes. • The intensity of satellite structures in XPS indicated the amount of charge transferred. • Single crystal structure of [Rh(Fctpy) 2 ][PF 6 ] 3. Abstract A series of 4′-ferrocenyl-2,2′:6′,2′'-terpyridine coordination metal complexes, [M(Fctpy) 2 ][PF 6 ] x with M = Co (2), Fe (3), and Rh (4) and x = 2 (for 2 and 3) or 3 (for 4), was subjected to an electrochemical and X-ray photoelectron spectroscopic study. The formal reduction potential of the Fc/Fc+ couple of the ferrocenyl-moiety (FeII) is related to the Allred Rochow electronegativities of the different coordinated metals, as well as with binding energies of the Fe 2p 3/2 photoelectron lines (as measured by XPS). The binding energy position of the main Fe 2p 3/2 photoelectron line, spin–orbit splitting between the main and satellite structure (charge transfer band) of the Fe 2p 3/2 photoelectron line as well as the intensity ratio between the of the main and satellite structure of the Fe 2p 3/2 photoelectron line (I ratio , this gives the relative amount of charge being transferred) gave insight in the electronic structure of these ferrocenyl-terpyridine coordination metal complexes, 2 – 4. A single crystal X-ray structure determination of 4 highlighted the disorder of the PF 6 counter anions as well as double occupancy of the central metal atom of Rh (in 4) with Fe, the Fe:Rh ratio is 0.14:0.85. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00201693
- Volume :
- 482
- Database :
- Academic Search Index
- Journal :
- Inorganica Chimica Acta
- Publication Type :
- Academic Journal
- Accession number :
- 131563091
- Full Text :
- https://doi.org/10.1016/j.ica.2018.04.013