Add time:08/16/2019         Source:sciencedirect.com

A series of 4′-ferrocenyl-2,2′:6′,2′'-terpyridine coordination metal complexes, [M(Fctpy)2][PF6]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 2p3/2 photoelectron lines (as measured by XPS).The binding energy position of the main Fe 2p3/2 photoelectron line, spin–orbit splitting between the main and satellite structure (charge transfer band) of the Fe 2p3/2 photoelectron line as well as the intensity ratio between the of the main and satellite structure of the Fe 2p3/2 photoelectron line (Iratio, 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 PF6 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.

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