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Article: Electronic spectroscopy, photophysical properties, and emission quenching studies of an oxidatively robust perfluorinated platinum porphyrin

TitleElectronic spectroscopy, photophysical properties, and emission quenching studies of an oxidatively robust perfluorinated platinum porphyrin
Authors
Issue Date2004
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2004, v. 43 n. 12, p. 3724-3732 How to Cite?
AbstractThe highly electron-deficient, β-octafluorinated meso-tetrakis(pentafluorophenyl)-porphyrin (H2F28TPP) was metalated with platinum to afford the oxidatively robust luminophore [PtF 28TPP], and its X-ray structure shows that the porphyrin core exists in a slightly saddle-shaped conformation. The absorption spectrum of [PtF 28TPP] in CH2Cl2 displays a near-UV Soret band (B) at 383 nm (ε = 2.85 × 108 dm3 mol -1 cm-1) and two visible Q(1,0) and Q(0,0) bands at 501 (ε = 1.45 × 104 dm3 mol-1 cm -1) and 533 (ε = 1.36 × 104 dm3 mol-1 cm-1) nm, respectively. These absorption bands of [PtF28TPP] are blue-shifted from those in [PtF20TPP] (390, 504, and 538 nm, respectively) and [PtTPP] (401, 509, and 539 nm, respectively). Excitation of [PtF28TPP] (complex concentration = 1.5 × 10-6 mol dm-3) in dichloromethane at the Soret or Q(1,0) or Q(0,0) band gave a phosphorescence with peak maximum at 650 nm (lifetime = 5.8 μs) and a weak shoulder at 712 nm. Both the emission lifetime and quantum yield vary with solvent polarity, and plots of τ versus EK and Φ versus EK (where EK is the empirical solvent polarity parameter based on the hypsochromic shift of the longest wavelength absorption of the [Mo(CO)4{(C5H 4N)HC=NCH2C6H5}] complex with increasing solvent polarity; see: Kamlet, M. J.; Abboud, J. L. M.; Taft, R. W. Prog. Phys. Org. Chem. 1981, 13, pp 485-630) show linear correlation, indicating that the emission is sensitive to the local environment/ medium. Electrochemical studies on [PtF28TPP] by cyclic voltammetry showed no porphyrin-centered oxidation at potential ≤ 1.5 V versus Ag/AgNO 3, demonstrating that [PtF28TPP] is more resistant toward oxidation than PtF20- TPP] (E1/2 = 1.33 V) and [PtTPP] (E1/2 = 0.97 V). The porphyrin-centered reduction of [PtF 28TPP] occurs at -0.75 and -1.18 V, which is anodically shifted from those at -1.06 and -1.55 V in [PtF20TPP], and -1.51 V in [PtTPP], respectively. The excited-state reduction potential of [PtF28TPP] is estimated to be 1.49 V versus Ag/AgNO3. Over 97% of the emission intensity of [PtF28TPP] was retained after irradiation with a high power mercury arc lamp (500 W) for 14 h, compared to 90% and 12% for [PtF 20TPP] and [PtTPP], respectively; hence, [PtF28TPP] exhibits superior photostability. Quenching of the emission of [PtF 28TPP] by oxygen, alcohol, catechol, and butylamine reveals that [PtF28TPP] is an oxidatively robust material with medium-sensitive photoluminescence properties.
Persistent Identifierhttp://hdl.handle.net/10722/69029
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLai, SWen_HK
dc.contributor.authorHou, YJen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorPang, HLen_HK
dc.contributor.authorWong, KYen_HK
dc.contributor.authorChang, CKen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2010-09-06T06:09:54Z-
dc.date.available2010-09-06T06:09:54Z-
dc.date.issued2004en_HK
dc.identifier.citationInorganic Chemistry, 2004, v. 43 n. 12, p. 3724-3732en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69029-
dc.description.abstractThe highly electron-deficient, β-octafluorinated meso-tetrakis(pentafluorophenyl)-porphyrin (H2F28TPP) was metalated with platinum to afford the oxidatively robust luminophore [PtF 28TPP], and its X-ray structure shows that the porphyrin core exists in a slightly saddle-shaped conformation. The absorption spectrum of [PtF 28TPP] in CH2Cl2 displays a near-UV Soret band (B) at 383 nm (ε = 2.85 × 108 dm3 mol -1 cm-1) and two visible Q(1,0) and Q(0,0) bands at 501 (ε = 1.45 × 104 dm3 mol-1 cm -1) and 533 (ε = 1.36 × 104 dm3 mol-1 cm-1) nm, respectively. These absorption bands of [PtF28TPP] are blue-shifted from those in [PtF20TPP] (390, 504, and 538 nm, respectively) and [PtTPP] (401, 509, and 539 nm, respectively). Excitation of [PtF28TPP] (complex concentration = 1.5 × 10-6 mol dm-3) in dichloromethane at the Soret or Q(1,0) or Q(0,0) band gave a phosphorescence with peak maximum at 650 nm (lifetime = 5.8 μs) and a weak shoulder at 712 nm. Both the emission lifetime and quantum yield vary with solvent polarity, and plots of τ versus EK and Φ versus EK (where EK is the empirical solvent polarity parameter based on the hypsochromic shift of the longest wavelength absorption of the [Mo(CO)4{(C5H 4N)HC=NCH2C6H5}] complex with increasing solvent polarity; see: Kamlet, M. J.; Abboud, J. L. M.; Taft, R. W. Prog. Phys. Org. Chem. 1981, 13, pp 485-630) show linear correlation, indicating that the emission is sensitive to the local environment/ medium. Electrochemical studies on [PtF28TPP] by cyclic voltammetry showed no porphyrin-centered oxidation at potential ≤ 1.5 V versus Ag/AgNO 3, demonstrating that [PtF28TPP] is more resistant toward oxidation than PtF20- TPP] (E1/2 = 1.33 V) and [PtTPP] (E1/2 = 0.97 V). The porphyrin-centered reduction of [PtF 28TPP] occurs at -0.75 and -1.18 V, which is anodically shifted from those at -1.06 and -1.55 V in [PtF20TPP], and -1.51 V in [PtTPP], respectively. The excited-state reduction potential of [PtF28TPP] is estimated to be 1.49 V versus Ag/AgNO3. Over 97% of the emission intensity of [PtF28TPP] was retained after irradiation with a high power mercury arc lamp (500 W) for 14 h, compared to 90% and 12% for [PtF 20TPP] and [PtTPP], respectively; hence, [PtF28TPP] exhibits superior photostability. Quenching of the emission of [PtF 28TPP] by oxygen, alcohol, catechol, and butylamine reveals that [PtF28TPP] is an oxidatively robust material with medium-sensitive photoluminescence properties.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleElectronic spectroscopy, photophysical properties, and emission quenching studies of an oxidatively robust perfluorinated platinum porphyrinen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=43&spage=3724&epage=3732&date=2004&atitle=Electronic+spectroscopy,+photophysical+properties,+and+emission+quenching+studies+of+an+oxidatively+robust+perfluorinated+platinum+porphyrin+en_HK
dc.identifier.emailLai, SW: swlai@hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityLai, SW=rp00717en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic049902hen_HK
dc.identifier.scopuseid_2-s2.0-2942605723en_HK
dc.identifier.hkuros91621en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-2942605723&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume43en_HK
dc.identifier.issue12en_HK
dc.identifier.spage3724en_HK
dc.identifier.epage3732en_HK
dc.identifier.isiWOS:000221989000025-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLai, SW=7402937200en_HK
dc.identifier.scopusauthoridHou, YJ=7402198922en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridPang, HL=8407231300en_HK
dc.identifier.scopusauthoridWong, KY=7404760030en_HK
dc.identifier.scopusauthoridChang, CK=7407039448en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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