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Article: Luminescent nitridometal complexes. Photophysical and photochemical properties of the 3[(dxy)1(dπ*)1] excited state of nitridoosmium(VI) complexes with polypyridine ligands

TitleLuminescent nitridometal complexes. Photophysical and photochemical properties of the 3[(dxy)1(dπ*)1] excited state of nitridoosmium(VI) complexes with polypyridine ligands
Authors
Issue Date1995
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Journal Of The Chemical Society, Dalton Transactions, 1995 n. 4, p. 657-663 How to Cite?
Abstract
Nitridoosmium(VI) complexes of substituted 2,2′-bipyridines and 1,10-phenanthrolines have been prepared from [OsNCl4]- and the appropriate chelating ligands in acetonitrile. Reaction of [Os(bipy)NCl3](bipy = 2,2′-bipyridine) and [Os(terpy)NCl2]Cl (terpy = 2,2′:6′,2″-terpyridine) with neat trifluoromethanesulfonic acid gave [Os(bipy)NCl2(H2O)]+ and [Os(terpy)N(Cl)(CF3SO3)]+ respectively. The crystal structures of [Os(dmbipy)NCl3](dmbipy = 5,5′-dimethyl-2,2′-bipyridine), [Os(bipy)NCl2(H2O)]+ and [Os(terpy)N(Cl)(CF3SO3)]+ show that the Os≡N distances are 1.68(1), 1.630(7) and 1.629(8) Å respectively. In the latter two complexes the Os≡N moiety is perpendicular to the plane of the chelating ligand. The spectroscopic, photophysical and photochemical properties of the newly prepared complexes have been studied. All have long-lived and emissive 3[dxy′,dπ.] excited states in the solid state and in fluid solution at room temperature. The complex mer-[Os(terpy)NCl2][ClO4] has the longest emission lifetime 4.64 μs (at infinite dilution) in degassed acetonitrile at room temperature. Based on quenching studies with aromatic hydrocarbons, this complex is a powerful photooxidant with E⊖[OsVI*-OsV] being 2.12(30)V vs. the normal hydrogen electrode.
Persistent Identifierhttp://hdl.handle.net/10722/168256
ISSN
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChin, KFen_US
dc.contributor.authorCheung, KKen_US
dc.contributor.authorYip, HKen_US
dc.contributor.authorMak, TCWen_US
dc.contributor.authorChe, CMen_US
dc.date.accessioned2012-10-08T03:16:44Z-
dc.date.available2012-10-08T03:16:44Z-
dc.date.issued1995en_US
dc.identifier.citationJournal Of The Chemical Society, Dalton Transactions, 1995 n. 4, p. 657-663en_US
dc.identifier.issn1472-7773en_US
dc.identifier.urihttp://hdl.handle.net/10722/168256-
dc.description.abstractNitridoosmium(VI) complexes of substituted 2,2′-bipyridines and 1,10-phenanthrolines have been prepared from [OsNCl4]- and the appropriate chelating ligands in acetonitrile. Reaction of [Os(bipy)NCl3](bipy = 2,2′-bipyridine) and [Os(terpy)NCl2]Cl (terpy = 2,2′:6′,2″-terpyridine) with neat trifluoromethanesulfonic acid gave [Os(bipy)NCl2(H2O)]+ and [Os(terpy)N(Cl)(CF3SO3)]+ respectively. The crystal structures of [Os(dmbipy)NCl3](dmbipy = 5,5′-dimethyl-2,2′-bipyridine), [Os(bipy)NCl2(H2O)]+ and [Os(terpy)N(Cl)(CF3SO3)]+ show that the Os≡N distances are 1.68(1), 1.630(7) and 1.629(8) Å respectively. In the latter two complexes the Os≡N moiety is perpendicular to the plane of the chelating ligand. The spectroscopic, photophysical and photochemical properties of the newly prepared complexes have been studied. All have long-lived and emissive 3[dxy′,dπ.] excited states in the solid state and in fluid solution at room temperature. The complex mer-[Os(terpy)NCl2][ClO4] has the longest emission lifetime 4.64 μs (at infinite dilution) in degassed acetonitrile at room temperature. Based on quenching studies with aromatic hydrocarbons, this complex is a powerful photooxidant with E⊖[OsVI*-OsV] being 2.12(30)V vs. the normal hydrogen electrode.en_US
dc.languageengen_US
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_US
dc.relation.ispartofJournal of the Chemical Society, Dalton Transactionsen_US
dc.titleLuminescent nitridometal complexes. Photophysical and photochemical properties of the 3[(dxy)1(dπ*)1] excited state of nitridoosmium(VI) complexes with polypyridine ligandsen_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1039/DT9950000657en_US
dc.identifier.scopuseid_2-s2.0-37049090714en_US
dc.identifier.hkuros1457-
dc.identifier.issue4en_US
dc.identifier.spage657en_US
dc.identifier.epage663en_US
dc.identifier.isiWOS:A1995QH76300021-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridChin, KF=23066279000en_US
dc.identifier.scopusauthoridCheung, KK=7402406613en_US
dc.identifier.scopusauthoridYip, HK=15068942100en_US
dc.identifier.scopusauthoridMak, TCW=7401931058en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US

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