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Article: Electroswitchable Photoluminescence Activity: Synthesis, Spectroscopy, Electrochemistry, Photophysics, and X-ray Crystal and Electronic Structures of [Re(bpy)(CO)3(C≡C-C6H4-C≡C)Fe(C5Me5)(dppe)][PF6]n (n = 0, 1)

TitleElectroswitchable Photoluminescence Activity: Synthesis, Spectroscopy, Electrochemistry, Photophysics, and X-ray Crystal and Electronic Structures of [Re(bpy)(CO)3(C≡C-C6H4-C≡C)Fe(C5Me5)(dppe)][PF6]n (n = 0, 1)
Authors
Issue Date2003
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2003, v. 42 n. 22, p. 7086-7097 How to Cite?
AbstractA novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO) 3(C≡C-C 6H 4-C≡C)Fe(C 5Me 5)(dppe)], 1, and its oxidized species, [Re(bpy)(CO) 3(C≡C-C 6H 4-C≡ C)Fe(C 5Me 5)(dppe)][PF 6], 2, have been synthesized and their X-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO) 3(C≡C-C 6H 4-(H)C=C)Fe-(C 5Me 5)(dppe)][PF 6], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows a quasireversible reduction couple at -1.49 V (vs SCE), a fully reversible oxidation at -0.19 V, and a quasireversible oxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen-substituted model complex Re(bpy)(CO) 3(C≡C-C 6H 4-C≡C)Fe(C 5H 5)(dHpe) (Cp = C 5H 5, dHpe = H 2P-(CH 2) 2-PH 2) (1-H) show that the LUMO is mainly bipyridine ligand π* in character while the HOMO is largely iron(II) d orbital in character. The electronic absorption spectrum of 1 shows low-energy absorption at 390 nm with a 420 nm shoulder in CH 2Cl 2, while that of 2 exhibits less intense low-energy bands at 432 and 474 nm and additional low-energy bands in the NIR at ca. 830, 1389, and 1773 nm. Unlike the related luminescent rhenium(I)-alkynyl complex [Re(bpy)(CO) 3(C≡C-C 6H 4-C≡C-H)], 4, complex 1 is found to be nonemissive, and such a phenomenon is attributed to an intramolecular quenching of the emissive dπ(Re)→π*(bpy) 3MLCT state by the low-lying MLCT and LF excited states of the iron moiety. Interestingly, switching on of the luminescence property derived from the dπ(Re)→π *(bpy) 3MLCT state can be demonstrated in the oxidized species 2 and the related vinylidene analogue 3 due to the absence of the quenching pathway.
Persistent Identifierhttp://hdl.handle.net/10722/167843
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorWong, KMCen_HK
dc.contributor.authorLam, SCFen_HK
dc.contributor.authorKo, CCen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorYam, VWWen_HK
dc.contributor.authorRoué, Sen_HK
dc.contributor.authorLapinte, Cen_HK
dc.contributor.authorFathallah, Sen_HK
dc.contributor.authorCostuas, Ken_HK
dc.contributor.authorKahlal, Sen_HK
dc.contributor.authorHalet, JFen_HK
dc.date.accessioned2012-10-08T03:12:08Z-
dc.date.available2012-10-08T03:12:08Z-
dc.date.issued2003en_HK
dc.identifier.citationInorganic Chemistry, 2003, v. 42 n. 22, p. 7086-7097en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167843-
dc.description.abstractA novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO) 3(C≡C-C 6H 4-C≡C)Fe(C 5Me 5)(dppe)], 1, and its oxidized species, [Re(bpy)(CO) 3(C≡C-C 6H 4-C≡ C)Fe(C 5Me 5)(dppe)][PF 6], 2, have been synthesized and their X-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO) 3(C≡C-C 6H 4-(H)C=C)Fe-(C 5Me 5)(dppe)][PF 6], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows a quasireversible reduction couple at -1.49 V (vs SCE), a fully reversible oxidation at -0.19 V, and a quasireversible oxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen-substituted model complex Re(bpy)(CO) 3(C≡C-C 6H 4-C≡C)Fe(C 5H 5)(dHpe) (Cp = C 5H 5, dHpe = H 2P-(CH 2) 2-PH 2) (1-H) show that the LUMO is mainly bipyridine ligand π* in character while the HOMO is largely iron(II) d orbital in character. The electronic absorption spectrum of 1 shows low-energy absorption at 390 nm with a 420 nm shoulder in CH 2Cl 2, while that of 2 exhibits less intense low-energy bands at 432 and 474 nm and additional low-energy bands in the NIR at ca. 830, 1389, and 1773 nm. Unlike the related luminescent rhenium(I)-alkynyl complex [Re(bpy)(CO) 3(C≡C-C 6H 4-C≡C-H)], 4, complex 1 is found to be nonemissive, and such a phenomenon is attributed to an intramolecular quenching of the emissive dπ(Re)→π*(bpy) 3MLCT state by the low-lying MLCT and LF excited states of the iron moiety. Interestingly, switching on of the luminescence property derived from the dπ(Re)→π *(bpy) 3MLCT state can be demonstrated in the oxidized species 2 and the related vinylidene analogue 3 due to the absence of the quenching pathway.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleElectroswitchable Photoluminescence Activity: Synthesis, Spectroscopy, Electrochemistry, Photophysics, and X-ray Crystal and Electronic Structures of [Re(bpy)(CO)3(C≡C-C6H4-C≡C)Fe(C5Me5)(dppe)][PF6]n (n = 0, 1)en_HK
dc.typeArticleen_HK
dc.identifier.emailWong, KMC: wongmc@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailYam, VWW: wwyam@hku.hken_HK
dc.identifier.authorityWong, KMC=rp00809en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityYam, VWW=rp00822en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic030226den_HK
dc.identifier.pmid14577776-
dc.identifier.scopuseid_2-s2.0-0242300740en_HK
dc.identifier.hkuros91287-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0242300740&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume42en_HK
dc.identifier.issue22en_HK
dc.identifier.spage7086en_HK
dc.identifier.epage7097en_HK
dc.identifier.isiWOS:000186286600024-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridWong, KMC=8061067200en_HK
dc.identifier.scopusauthoridLam, SCF=7402279761en_HK
dc.identifier.scopusauthoridKo, CC=7202596455en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridYam, VWW=18539304700en_HK
dc.identifier.scopusauthoridRoué, S=6506126291en_HK
dc.identifier.scopusauthoridLapinte, C=55187017600en_HK
dc.identifier.scopusauthoridFathallah, S=6508159617en_HK
dc.identifier.scopusauthoridCostuas, K=6602330879en_HK
dc.identifier.scopusauthoridKahlal, S=6603609986en_HK
dc.identifier.scopusauthoridHalet, JF=7004456950en_HK

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