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Article: Vibrational spectra of dipyrido[3,2-a:2′,3′-c]phenazine and its radical anion analyzed by Ab initio calculations and deuteration studies

TitleVibrational spectra of dipyrido[3,2-a:2′,3′-c]phenazine and its radical anion analyzed by Ab initio calculations and deuteration studies
Authors
Issue Date2002
PublisherChemical Society of Japan. The Journal's web site is located at http://www.chemistry.or.jp/journals/bcsj/index-e.html
Citation
Bulletin Of The Chemical Society Of Japan, 2002, v. 75 n. 5, p. 933-942 How to Cite?
AbstractThe ligand dipyrido[3,2-a:2′,3′-c]phenazine (dppz) and its deuterated analogues, d4-dppz, d6-dppz, d10-dppz, and [ReCl(CO)3] complexes with these ligands have been synthesized. Using DFT calculations it is possible to calculate a geometry of the ligand such that it matches the crystallographic data for a variety of dppz complexes. B3LYP/6-31G(d) frequency calculations correspond closely to the experimental IR and Raman data. Analysis of the calculated normal modes of vibration reveals the presence of a number of modes that are localized to the ring sections of the dppz-framework. Modes 79, 78, 77, 50, and 49, which lie at 1602, 1586, 1576, 1071, and 1034 cm-1, respectively, in the experimental spectra of dppz correspond to phenanthroline-based modes. Modes 68 and 67, lying at 1414 and 1402 cm-1 in dppz are phenazine-based vibrations. These provide an insight into the nature of the MLCT transitions for metal complexes with dppz. The preferential enhancement of phenanthroline-based modes in the resonance Raman spectra of these complexes strongly suggests the π* accepting MO is of phenanthroline character. DFT calculations (B3LYP/6-31G(d)) on the radical anion reveal the elongation of bonds about the pyrimidine ring. The frequency calculations also reveal significant changes in the vibrational spectra for dppz•- from the neutral ligand. Experimental resonance Raman data for the electrochemically reduced [ReCl(CO)3(dppz)]- and the deuterated analogues show distinct isotope shifts that may be correlated to results obtained from the calculations. The characteristic bands observed in these spectra are phenanthroline-based. They may be correlated with time-resolved resonance Raman spectra of Ru(II) and Re(I) complexes.
Persistent Identifierhttp://hdl.handle.net/10722/167730
ISSN
2015 Impact Factor: 1.372
2015 SCImago Journal Rankings: 0.614
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorMatthewson, BJen_US
dc.contributor.authorFlood, Aen_US
dc.contributor.authorPolson, MIJen_US
dc.contributor.authorArmstrong, Cen_US
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorGordon, KCen_US
dc.date.accessioned2012-10-08T03:10:33Z-
dc.date.available2012-10-08T03:10:33Z-
dc.date.issued2002en_US
dc.identifier.citationBulletin Of The Chemical Society Of Japan, 2002, v. 75 n. 5, p. 933-942en_US
dc.identifier.issn0009-2673en_US
dc.identifier.urihttp://hdl.handle.net/10722/167730-
dc.description.abstractThe ligand dipyrido[3,2-a:2′,3′-c]phenazine (dppz) and its deuterated analogues, d4-dppz, d6-dppz, d10-dppz, and [ReCl(CO)3] complexes with these ligands have been synthesized. Using DFT calculations it is possible to calculate a geometry of the ligand such that it matches the crystallographic data for a variety of dppz complexes. B3LYP/6-31G(d) frequency calculations correspond closely to the experimental IR and Raman data. Analysis of the calculated normal modes of vibration reveals the presence of a number of modes that are localized to the ring sections of the dppz-framework. Modes 79, 78, 77, 50, and 49, which lie at 1602, 1586, 1576, 1071, and 1034 cm-1, respectively, in the experimental spectra of dppz correspond to phenanthroline-based modes. Modes 68 and 67, lying at 1414 and 1402 cm-1 in dppz are phenazine-based vibrations. These provide an insight into the nature of the MLCT transitions for metal complexes with dppz. The preferential enhancement of phenanthroline-based modes in the resonance Raman spectra of these complexes strongly suggests the π* accepting MO is of phenanthroline character. DFT calculations (B3LYP/6-31G(d)) on the radical anion reveal the elongation of bonds about the pyrimidine ring. The frequency calculations also reveal significant changes in the vibrational spectra for dppz•- from the neutral ligand. Experimental resonance Raman data for the electrochemically reduced [ReCl(CO)3(dppz)]- and the deuterated analogues show distinct isotope shifts that may be correlated to results obtained from the calculations. The characteristic bands observed in these spectra are phenanthroline-based. They may be correlated with time-resolved resonance Raman spectra of Ru(II) and Re(I) complexes.en_US
dc.languageengen_US
dc.publisherChemical Society of Japan. The Journal's web site is located at http://www.chemistry.or.jp/journals/bcsj/index-e.htmlen_US
dc.relation.ispartofBulletin of the Chemical Society of Japanen_US
dc.titleVibrational spectra of dipyrido[3,2-a:2′,3′-c]phenazine and its radical anion analyzed by Ab initio calculations and deuteration studiesen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1246/bcsj.75.933en_US
dc.identifier.scopuseid_2-s2.0-0036089119en_US
dc.identifier.hkuros73894-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0036089119&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume75en_US
dc.identifier.issue5en_US
dc.identifier.spage933en_US
dc.identifier.epage942en_US
dc.identifier.isiWOS:000175911800008-
dc.publisher.placeJapanen_US
dc.identifier.scopusauthoridMatthewson, BJ=8112540300en_US
dc.identifier.scopusauthoridFlood, A=7006079520en_US
dc.identifier.scopusauthoridPolson, MIJ=6701492678en_US
dc.identifier.scopusauthoridArmstrong, C=8410216000en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US
dc.identifier.scopusauthoridGordon, KC=7202357498en_US

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