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Article: Spectroscopic properties of luminescent platinum(II) complexes containing 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine (tBu3tpy). Crystal structures of [Pt(tBu3tpy)Cl]ClO4 and [Pt(tBu3tpy){CH2C(O)Me}]ClO4

TitleSpectroscopic properties of luminescent platinum(II) complexes containing 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine (tBu3tpy). Crystal structures of [Pt(tBu3tpy)Cl]ClO4 and [Pt(tBu3tpy){CH2C(O)Me}]ClO4
Authors
Issue Date1999
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1999, v. 38 n. 19, p. 4262-4267 How to Cite?
AbstractThe 77 K emission spectrum of [Pt(tBu3tpy)Cl]ClO4, 1(ClO4) (tBu3tpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine), in a 10-3 mol dm-3 MeOH/EtOH glassy solution exhibits a 625 nm band attributed to tBu3tpy π-π interactions, whereas a dilute solution (10-6 mol dm-3) shows a vibronic intraligand emission at λmax 467 nm. By comparing the UV-vis spectra of 1 with the 1IL-dominated spectrum of [Au(tBu3tpy)Cl]2+ (4) in CH3CN, the moderately intense absorption band at λmax 373-386 nm for the former is ascribed to a 1MLCT [(5d)Pt → π*(tBu3tpy)] transition. The absorption spectrum of 1 contains a weak shoulder at 465 nm (∈ = 57 dm3 mol-1 cm-1) which obeys Beer's law in the concentration range 5 × 10-4 to 1 × 10-2 mol dm-3, and a 3MLCT assignment is proposed. Ketonyl platinum(II) complexes [Pt(tBu3tpy){CH2C(O)R}]ClO4 (R = Me, 2 and R = Ph, 3) have been prepared from 1(ClO4) in the presence of aqueous NaOH and the corresponding methyl ketone. The molecular structures of 1(ClO4) and 2(ClO4)·C2H5OH reveal π-stacking orientations for the tBu3tpy ligands with interplanar separations of ca. 3.8 and 3.6 Å, respectively. Complexes 2 and 3 are luminescent in solution at room temperature, and 3MLCT excited states are assigned, while 1 is nonemissive. The superior photophysical properties of 2 and 3 are ascribed to the stronger σ-donating ability of the ketonyl ligands. Like 1, complexes 2 and 3 also display low-energy emission at ca. 620 nm in 10-3 mol dm-3 MeOH/EtOH glass at 77 K. Complex 1(ClO4) is emissive in crystalline form at 77 K only (λmax 560 nm). Solid-state emissions of 2(ClO4) and 3(ClO4) at room temperature (λmax 607 and 615 nm, respectively) are derived from weak stacking interactions between tBu3tpy groups, while their emission maxima are red-shifted at 77 K. © 1999 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167320
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.authorChan, MCWen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2012-10-08T03:05:37Z-
dc.date.available2012-10-08T03:05:37Z-
dc.date.issued1999en_HK
dc.identifier.citationInorganic Chemistry, 1999, v. 38 n. 19, p. 4262-4267en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167320-
dc.description.abstractThe 77 K emission spectrum of [Pt(tBu3tpy)Cl]ClO4, 1(ClO4) (tBu3tpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine), in a 10-3 mol dm-3 MeOH/EtOH glassy solution exhibits a 625 nm band attributed to tBu3tpy π-π interactions, whereas a dilute solution (10-6 mol dm-3) shows a vibronic intraligand emission at λmax 467 nm. By comparing the UV-vis spectra of 1 with the 1IL-dominated spectrum of [Au(tBu3tpy)Cl]2+ (4) in CH3CN, the moderately intense absorption band at λmax 373-386 nm for the former is ascribed to a 1MLCT [(5d)Pt → π*(tBu3tpy)] transition. The absorption spectrum of 1 contains a weak shoulder at 465 nm (∈ = 57 dm3 mol-1 cm-1) which obeys Beer's law in the concentration range 5 × 10-4 to 1 × 10-2 mol dm-3, and a 3MLCT assignment is proposed. Ketonyl platinum(II) complexes [Pt(tBu3tpy){CH2C(O)R}]ClO4 (R = Me, 2 and R = Ph, 3) have been prepared from 1(ClO4) in the presence of aqueous NaOH and the corresponding methyl ketone. The molecular structures of 1(ClO4) and 2(ClO4)·C2H5OH reveal π-stacking orientations for the tBu3tpy ligands with interplanar separations of ca. 3.8 and 3.6 Å, respectively. Complexes 2 and 3 are luminescent in solution at room temperature, and 3MLCT excited states are assigned, while 1 is nonemissive. The superior photophysical properties of 2 and 3 are ascribed to the stronger σ-donating ability of the ketonyl ligands. Like 1, complexes 2 and 3 also display low-energy emission at ca. 620 nm in 10-3 mol dm-3 MeOH/EtOH glass at 77 K. Complex 1(ClO4) is emissive in crystalline form at 77 K only (λmax 560 nm). Solid-state emissions of 2(ClO4) and 3(ClO4) at room temperature (λmax 607 and 615 nm, respectively) are derived from weak stacking interactions between tBu3tpy groups, while their emission maxima are red-shifted at 77 K. © 1999 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.titleSpectroscopic properties of luminescent platinum(II) complexes containing 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine (tBu3tpy). Crystal structures of [Pt(tBu3tpy)Cl]ClO4 and [Pt(tBu3tpy){CH2C(O)Me}]ClO4en_HK
dc.typeArticleen_HK
dc.identifier.emailLai, SW: swlai@hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityLai, SW=rp00717en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic990446k-
dc.identifier.scopuseid_2-s2.0-0001096807en_HK
dc.identifier.hkuros51138-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0001096807&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume38en_HK
dc.identifier.issue19en_HK
dc.identifier.spage4262en_HK
dc.identifier.epage4267en_HK
dc.identifier.isiWOS:000082713600015-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLai, SW=7402937200en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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