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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
Title | 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 |
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Authors | |
Issue Date | 1999 |
Publisher | American 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? |
Abstract | The 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 Identifier | http://hdl.handle.net/10722/167320 |
ISSN | 2023 Impact Factor: 4.3 2023 SCImago Journal Rankings: 0.928 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Lai, SW | en_HK |
dc.contributor.author | Chan, MCW | en_HK |
dc.contributor.author | Cheung, KK | en_HK |
dc.contributor.author | Che, CM | en_HK |
dc.date.accessioned | 2012-10-08T03:05:37Z | - |
dc.date.available | 2012-10-08T03:05:37Z | - |
dc.date.issued | 1999 | en_HK |
dc.identifier.citation | Inorganic Chemistry, 1999, v. 38 n. 19, p. 4262-4267 | en_HK |
dc.identifier.issn | 0020-1669 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/167320 | - |
dc.description.abstract | The 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic | en_HK |
dc.relation.ispartof | Inorganic Chemistry | en_HK |
dc.title | 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 | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Lai, SW: swlai@hku.hk | en_HK |
dc.identifier.email | Che, CM: cmche@hku.hk | en_HK |
dc.identifier.authority | Lai, SW=rp00717 | en_HK |
dc.identifier.authority | Che, CM=rp00670 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ic990446k | - |
dc.identifier.scopus | eid_2-s2.0-0001096807 | en_HK |
dc.identifier.hkuros | 51138 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0001096807&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 38 | en_HK |
dc.identifier.issue | 19 | en_HK |
dc.identifier.spage | 4262 | en_HK |
dc.identifier.epage | 4267 | en_HK |
dc.identifier.isi | WOS:000082713600015 | - |
dc.publisher.place | United States | en_HK |
dc.identifier.scopusauthorid | Lai, SW=7402937200 | en_HK |
dc.identifier.scopusauthorid | Chan, MCW=7402598116 | en_HK |
dc.identifier.scopusauthorid | Cheung, KK=7402406613 | en_HK |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_HK |
dc.identifier.issnl | 0020-1669 | - |