dc.contributor.author |
Earles, JC |
en |
dc.contributor.author |
Gordon, KC |
en |
dc.contributor.author |
Stephenson, AWI |
en |
dc.contributor.author |
Partridge, Ashton |
en |
dc.contributor.author |
Officer, DL |
en |
dc.date.accessioned |
2011-11-29T19:01:24Z |
en |
dc.date.issued |
2011 |
en |
dc.identifier.citation |
Physical Chemistry Chemical Physics 13(4):1597-1605 2011 |
en |
dc.identifier.issn |
1463-9076 |
en |
dc.identifier.uri |
http://hdl.handle.net/2292/9607 |
en |
dc.description.abstract |
A series of tetraphenylporphyrins appended at the b-pyrrolic position with an ethynylphenyleneor ethynylpyridine-substituent have been subjected to spectroscopic and density functional theory (DFT) analyses. The mean absolute deviation between corresponding experimental and DFT-derived vibrational spectra is up to 10.2 cm 1 , suggesting that the DFT B3LYP/6-31G(d) method provides an accurate model of the b-substituted porphyrin systems. The configuration interactions that give rise to prominent electronic absorptions have been calculated using time-dependant DFT (TD-DFT) and have been rationalized with reference to the energy and topology of DFT calculated molecular orbitals. As the electron withdrawing capacity of the b-substituent increases the LUMO orbital gains appreciable amplitude over the substituent moiety and is stabilised. This represents a departure from the assumptions underpinning the Gouterman four-orbital model, resulting in atypical electronic absorption spectra. This phenomenon is also manifested in the enhancement patterns of the resonance Raman spectra insofar as B-band excitation engenders an enhancement of substituent based modes. These observations demonstrate that the b-substituent exerts an appreciable electronic influence on the porphyrin p-electron system and provides a means of introducing charge-transfer character to prominent electronic transitions. |
en |
dc.publisher |
Royal Society of Chemistry |
en |
dc.relation.ispartofseries |
Physical Chemistry Chemical Physics |
en |
dc.rights |
Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. Details obtained from
http://www.sherpa.ac.uk/romeo/issn/1463-9076/ |
en |
dc.rights.uri |
https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm |
en |
dc.title |
Spectroscopic and computational study of β-ethynylphenylene substituted zinc and free-base porphyrins |
en |
dc.type |
Journal Article |
en |
dc.identifier.doi |
10.1039/c0cp01113d |
en |
pubs.issue |
4 |
en |
pubs.begin-page |
1597 |
en |
pubs.volume |
13 |
en |
dc.rights.holder |
Copyright: the Owner Societies |
en |
dc.identifier.pmid |
21125110 |
en |
pubs.end-page |
1605 |
en |
dc.rights.accessrights |
http://purl.org/eprint/accessRights/RestrictedAccess |
en |
pubs.subtype |
Article |
en |
pubs.elements-id |
219732 |
en |
pubs.org-id |
Engineering |
en |
pubs.org-id |
Chemical and Materials Eng |
en |
pubs.record-created-at-source-date |
2011-11-29 |
en |
pubs.dimensions-id |
21125110 |
en |