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Article: Electrogenerated chemiluminescence of platinum(II) alkynyl terpyridine complex with peroxydisulfate as coreactant

TitleElectrogenerated chemiluminescence of platinum(II) alkynyl terpyridine complex with peroxydisulfate as coreactant
Authors
Issue Date2011
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2011, v. 50 n. 6, p. 2125-2132 How to Cite?
AbstractA Pt(II) alkynyl terpyridine complex containing a carbazole moiety, [P( tBu 3tpy)(C=C-C 6H 4-4-carbazole-9)] + ( tBu 3tpy = 4,4',4"-tri-fert-butyl-2,2': 6',2"-terpyridine) 1, has been synthesized and characterized. The photophysical behavior has been studied, and the molecular structure has been determined by X-ray crystallography. The complex was found to exhibit intense electrogenerated chemiluminescence (ECL) using peroxydisulfate (S 2O 8 2-) as coreactant in acet-onitrile/water (1-25%, v/v) mixture at both glassy carbon and gold electrodes, representing the first ECL example of the Pt(II) alkynyl family. The ECL was produced at potential corresponding to the first reduction wave (-0.90 V vs SCE), significantly shifted by ∼0.65 V toward more positive potential compared with that of [Ru(bpy) 3] 2+ (bpy = 2,2'-bipyridine). The ECL spectrum was found to be identical to the photoluminescence spectrum recorded in the same medium, indicating the formation of the same excited state of dπ(Pt) → π *( tBu 3tpy) 3MLCT mixed with π(C=CR)→ π *( tBu 3tpy) 3LLCT in both cases. The ECL mechanism was proposed involving the formation of the strongly oxidizing intermediate, SO 4 •-, mainly generated during the catalytic reduction of S 2O 8 2-by the electrogenerated 1 -. Chemiluminescence of 1/S 2O 8 2- based on reduction with Al metal is also described. © 2011 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/135036
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
Funding AgencyGrant Number
University of Hong Kong
URC Strategic Research Theme on Molecular Materials
University Grants CommitteeAoE/P-03/08
Research Grants Council of Hong Kong Special Administrative Region, ChinaHKU 7076/10P
Funding Information:

We acknowledge support from The University of Hong Kong under the Distinguished Research Achievement Award Scheme and the URC Strategic Research Theme on Molecular Materials. This work has been supported by the University Grants Committee Areas of Excellence Scheme (AoE/P-03/08) and a General Research Fund (GRF) from the Research Grants Council of Hong Kong Special Administrative Region, China (HKU 7076/10P). Z.-F.C. and E.C.-H.K. acknowledge the receipt of postgraduate studentships from The University of Hong Kong.

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DC FieldValueLanguage
dc.contributor.authorChen, Zen_HK
dc.contributor.authorWong, KMCen_HK
dc.contributor.authorKwok, ECHen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorZu, Yen_HK
dc.contributor.authorYam, VWWen_HK
dc.date.accessioned2011-07-27T01:26:22Z-
dc.date.available2011-07-27T01:26:22Z-
dc.date.issued2011en_HK
dc.identifier.citationInorganic Chemistry, 2011, v. 50 n. 6, p. 2125-2132en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/135036-
dc.description.abstractA Pt(II) alkynyl terpyridine complex containing a carbazole moiety, [P( tBu 3tpy)(C=C-C 6H 4-4-carbazole-9)] + ( tBu 3tpy = 4,4',4"-tri-fert-butyl-2,2': 6',2"-terpyridine) 1, has been synthesized and characterized. The photophysical behavior has been studied, and the molecular structure has been determined by X-ray crystallography. The complex was found to exhibit intense electrogenerated chemiluminescence (ECL) using peroxydisulfate (S 2O 8 2-) as coreactant in acet-onitrile/water (1-25%, v/v) mixture at both glassy carbon and gold electrodes, representing the first ECL example of the Pt(II) alkynyl family. The ECL was produced at potential corresponding to the first reduction wave (-0.90 V vs SCE), significantly shifted by ∼0.65 V toward more positive potential compared with that of [Ru(bpy) 3] 2+ (bpy = 2,2'-bipyridine). The ECL spectrum was found to be identical to the photoluminescence spectrum recorded in the same medium, indicating the formation of the same excited state of dπ(Pt) → π *( tBu 3tpy) 3MLCT mixed with π(C=CR)→ π *( tBu 3tpy) 3LLCT in both cases. The ECL mechanism was proposed involving the formation of the strongly oxidizing intermediate, SO 4 •-, mainly generated during the catalytic reduction of S 2O 8 2-by the electrogenerated 1 -. Chemiluminescence of 1/S 2O 8 2- based on reduction with Al metal is also described. © 2011 American Chemical Society.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.subject.meshElectrochemistry-
dc.subject.meshLuminescence-
dc.subject.meshOrganoplatinum Compounds - chemical synthesis - chemistry-
dc.subject.meshPeroxides - chemistry-
dc.subject.meshSulfates - chemistry-
dc.titleElectrogenerated chemiluminescence of platinum(II) alkynyl terpyridine complex with peroxydisulfate as coreactanten_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_fulltext-
dc.identifier.doi10.1021/ic101119qen_HK
dc.identifier.pmid21341791-
dc.identifier.scopuseid_2-s2.0-79954445889en_HK
dc.identifier.hkuros186746en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-79954445889&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume50en_HK
dc.identifier.issue6en_HK
dc.identifier.spage2125en_HK
dc.identifier.epage2132en_HK
dc.identifier.isiWOS:000288182700019-
dc.publisher.placeUnited Statesen_HK
dc.relation.projectInstitute of Molecular Functional Materials-
dc.identifier.scopusauthoridChen, Z=22936679300en_HK
dc.identifier.scopusauthoridWong, KMC=8061067200en_HK
dc.identifier.scopusauthoridKwok, ECH=36652815700en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridZu, Y=7006348826en_HK
dc.identifier.scopusauthoridYam, VWW=18539304700en_HK

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