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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
Title | Vibrational spectra of dipyrido[3,2-a:2′,3′-c]phenazine and its radical anion analyzed by Ab initio calculations and deuteration studies |
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Authors | |
Issue Date | 2002 |
Publisher | Chemical 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? |
Abstract | The 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 Identifier | http://hdl.handle.net/10722/167730 |
ISSN | 2023 Impact Factor: 3.3 2023 SCImago Journal Rankings: 0.665 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Matthewson, BJ | en_US |
dc.contributor.author | Flood, A | en_US |
dc.contributor.author | Polson, MIJ | en_US |
dc.contributor.author | Armstrong, C | en_US |
dc.contributor.author | Phillips, DL | en_US |
dc.contributor.author | Gordon, KC | en_US |
dc.date.accessioned | 2012-10-08T03:10:33Z | - |
dc.date.available | 2012-10-08T03:10:33Z | - |
dc.date.issued | 2002 | en_US |
dc.identifier.citation | Bulletin Of The Chemical Society Of Japan, 2002, v. 75 n. 5, p. 933-942 | en_US |
dc.identifier.issn | 0009-2673 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167730 | - |
dc.description.abstract | The 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.language | eng | en_US |
dc.publisher | Chemical Society of Japan. The Journal's web site is located at http://www.chemistry.or.jp/journals/bcsj/index-e.html | en_US |
dc.relation.ispartof | Bulletin of the Chemical Society of Japan | en_US |
dc.title | Vibrational spectra of dipyrido[3,2-a:2′,3′-c]phenazine and its radical anion analyzed by Ab initio calculations and deuteration studies | en_US |
dc.type | Article | en_US |
dc.identifier.email | Phillips, DL:phillips@hku.hk | en_US |
dc.identifier.authority | Phillips, DL=rp00770 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1246/bcsj.75.933 | en_US |
dc.identifier.scopus | eid_2-s2.0-0036089119 | en_US |
dc.identifier.hkuros | 73894 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0036089119&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 75 | en_US |
dc.identifier.issue | 5 | en_US |
dc.identifier.spage | 933 | en_US |
dc.identifier.epage | 942 | en_US |
dc.identifier.isi | WOS:000175911800008 | - |
dc.publisher.place | Japan | en_US |
dc.identifier.scopusauthorid | Matthewson, BJ=8112540300 | en_US |
dc.identifier.scopusauthorid | Flood, A=7006079520 | en_US |
dc.identifier.scopusauthorid | Polson, MIJ=6701492678 | en_US |
dc.identifier.scopusauthorid | Armstrong, C=8410216000 | en_US |
dc.identifier.scopusauthorid | Phillips, DL=7404519365 | en_US |
dc.identifier.scopusauthorid | Gordon, KC=7202357498 | en_US |
dc.identifier.issnl | 0009-2673 | - |