Synthesis and Excited State Raman Spectroscopy of Sterically Crowded Ruthenium(II) Octaethyltetraphenylporphyrin

Abstract

Pyridine and CO adducts of RuIIOETPP (OETPP = 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphinato) have been prepared and characterized by absorption and resonance Raman (RR) spectroscopy. Ru → porphyrin back-bonding is evident from the ground state RR spectra. Skeletal mode frequency downshifts in RuIIOETPP(Py)2 relative to RuIIOETPP(CO)(Py) are comparable to those seen for the TPP (tetraphenylporphyrin) and OEP (octaethylporphyrin) analogs, indicating that distortion of the porphyrin ring from substituent crowding has little effect on the extent of back-bonding. Photoexcited RuIIOETPP(Py)2 has absorption and RR spectra which are similar to those of RuIITPP(Py)2 and are characteristic of a (dπ,π*) charge transfer state. As for RuIITPP(Py)2, the photoexcited RR spectrum has features indicating porphyrin anion formation and does not have pyridine anion features, as have been observed for photoexcited RuIIOEP(Py)2. The ethyl substituents raise the porphyrin eg* orbital above the lowest pyridine π* orbital in RuIIOEP(Py)2, but not in RuIIOETPP(Py)2, for which the effect of the phenyl substituents is dominant.