Please use this identifier to cite or link to this item: http://hdl.handle.net/20.500.12779/4692
DC FieldValueLanguage
dc.contributor.authorStulz, E.en_us
dc.contributor.authorSanders, J. K. M.en_us
dc.contributor.authorMontalti, M.en_us
dc.contributor.authorProdi, L.en_us
dc.contributor.authorZaccheroni, N.en_us
dc.contributor.authorFabrizi De Biani, Fabriziaen_us
dc.contributor.authorGrigiotti, E.en_us
dc.contributor.authorZanello, Pieroen_us
dc.date.accessioned2021-03-30T15:43:59Z-
dc.date.available2021-03-30T15:43:59Z-
dc.date.issued2002-
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/20.500.12779/4692-
dc.description40268en_US
dc.description.abstractThe photophysical and electrochemical properties of a series of mono- and bis-phosphine complexes of a 5,15-diphenyl-substituted ruthenium porphyrin, (MeOH)RuII(CO)(DPP) 1, were investigated. The ligands used were diphenyl(phenylacetenyl)phosphine (DPAP), diethyl (phenylacetenyl)phosphonite [PAP(OEt)2], tris(phenylacetenyl)phosphine [(PA)3P], and bis(diphenylphosphino)acetylene (DPPA). All complexes display two reversible one-electron oxidations at:  0.61 and 1.0 V vs SCE (1), 0.42−0.51 and 0.97−1.05 V [(PR3)RuII(CO)(DPP)], and 0.06−0.25 and 0.82−0.95 V [(PR3)2RuII(DPP)]. As predicted by EHMO calculations, the first oxidation is porphyrin or phosphorus centered, whereas the second one is ruthenium centered. Bulk electrolysis at the first oxidation potential yields stable monocations. Simulation of the cyclic voltammogram of (DPAP)RuII(CO)(DPP) in CH2Cl2 demonstrates the kinetic lability of the complex, and the association constant found (K = 1.27 × 106 M-1) is in accordance with the value determined by UV−vis titration (K = 1.2 ± 0.3 × 106 M-1). Coordination of one phosphine ligand to RuII(CO)(DPP) leads to a red shift in both the absorption and luminescence spectra. Shifts are typically 10 nm for the B- and Q-band absorptions and are not affected by the nature of the phosphorus ligand. The intense luminescence of (PR3)RuII(CO)(DPP), red-shifted by 21−28 nm compared to 1, can be attributed to originate from a 3(π,π*) excited state, and it exhibits lifetimes from 150 to 240 μs. In the bis-phosphine complexes (PR3)2RuII(DPP), the Q-band absorption is broadened and does not show any distinct peak. Judged from EHMO calculation, this could arise from a low-energy charge-transfer state involving the phosphorus ligand. The luminescence is efficiently quenched due to radiationless decay from a charge-transfer excited state, involving either the metal center or the phosphorus ligand; an unambiguous assignment could not be made.en_US
dc.language.isoenen_US
dc.relationNoneen_US
dc.relation.ispartofINORGANIC CHEMISTRYen_US
dc.titlePhosphine and phosphonite complexes of a Ru(II) porphyrin. 2. Photophysical and electrochemical studiesen_US
dc.typeArticleen_US
dc.identifier.doi10.1021/ic025728qen_US
dc.identifier.pmid12354061en_US
dc.identifier.scopus2-s2.0-0037037497en_US
dc.identifier.isiWOS:000178422600039en_US
dc.relation.volume41en_US
dc.relation.issue20en_US
dc.description.firstpage5269en_US
dc.description.lastpage5275en_US
dc.description.thirdmissionNot applicableen_US
item.cerifentitytypePublications-
item.grantfulltextnone-
item.languageiso639-1en-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.openairetypeArticle-
item.fulltextNo Fulltext-
crisitem.author.orcid0000-0002-1698-5858-
Appears in Collections:Publications
Show simple item record

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.