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

Vitols, S. E. and Roman, J. Scott and Ryan, Daniel E. and Blackwood, Milton E., Jr. and Sprio, Thomas G. (1997) Synthesis and Excited State Raman Spectroscopy of Sterically Crowded Ruthenium(II) Octaethyltetraphenylporphyrin. Inorganic Chemistry, 36 (5). pp. 764-769. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20180529-114824134

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Abstract

Pyridine and CO adducts of Ru^(II)OETPP (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 Ru^(II)OETPP(Py)_2 relative to Ru^(II)OETPP(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 Ru^(II)OETPP(Py)_2 has absorption and RR spectra which are similar to those of Ru^(II)TPP(Py)_2 and are characteristic of a (dπ,π*) charge transfer state. As for Ru^(II)TPP(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 Ru^(II)OEP(Py)_2. The ethyl substituents raise the porphyrin eg* orbital above the lowest pyridine π* orbital in Ru^(II)OEP(Py)_2, but not in Ru^(II)OETPP(Py)_2, for which the effect of the phenyl substituents is dominant.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ic960773hDOIArticle
Additional Information:© 1997 American Chemical Society. Received June 27, 1996. This work was supported by NIH Grant GM 33576.
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Funding AgencyGrant Number
NIHGM 33576
Issue or Number:5
Record Number:CaltechAUTHORS:20180529-114824134
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180529-114824134
Official Citation:Synthesis and Excited State Raman Spectroscopy of Sterically Crowded Ruthenium(II) Octaethyltetraphenylporphyrin S. E. Vitols, J. Scott Roman, Daniel E. Ryan, Milton E. Blackwood, Jr., and Thomas G. Spiro Inorganic Chemistry 1997 36 (5), 764-769 DOI: 10.1021/ic960773h
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86669
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:29 May 2018 20:15
Last Modified:03 Oct 2019 19:46

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