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- Publisher Website: 10.1002/1521-3765(20011105)7:21<4656::AID-CHEM4656>3.0.CO;2-D
- Scopus: eid_2-s2.0-0035813668
- PMID: 11757658
- WOS: WOS:000172133300015
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Article: Substrate-binding reactions of the 3[dσ*pσ] excited state of binuclear gold(I) complexes with bridging bis(dicyclohexylphosphino)methane ligands: Emission and time-resolved absorption spectroscopic studies
Title | Substrate-binding reactions of the 3[dσ*pσ] excited state of binuclear gold(I) complexes with bridging bis(dicyclohexylphosphino)methane ligands: Emission and time-resolved absorption spectroscopic studies |
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Authors | |
Keywords | Binuclear Complexes Exciplexes Gold Luminescence Quenching |
Issue Date | 2001 |
Publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry |
Citation | Chemistry - A European Journal, 2001, v. 7 n. 21, p. 4656-4664 How to Cite? |
Abstract | The complexes [Au 2(dcpm) 2]-Y 2 (dcpm = bis(dicyclohexylphosphino)-methane; Y = ClO 4 - (1), PF 6 - (2), CF 3SO 3 - (3), Au(CN) 2 - (4), Cl - (5), SCN - (6) and I - (7)) were prepared, and the structures of 1 and 4-7 were determined by X-ray crystallography. Complexes 1-4 display intense phosphorescence with λ max at 360-368 nm in the solid state at room temperature as well as in glassy solutions at 77 K. The solid-state emission quantum yields of the powdered samples are 0.37 (1), 0.74 (2), 0.53 (3) and 0.12 (4). Crystalline solid 5 displays both high-energy UV (λ max = 366 nm) and low-energy visible emissions (λ max = 505 nm) at room temperature, whereas either 6 or 7 shows only an intense emission with λ max at 465 or 473 nm, respectively. All the complexes in degassed acetonitrile solutions exhibit an intense phosphorescence with λ max ranging from 490 to 530 nm. The high-energy UV emission is assigned to the intrinsic emission of the 3[dσ*pσ] excited state of [Au 2(dcpm) 2] 2+, whereas the visible emission is attributed to the adduct formation of the triplet excited state with the solvent/counterion. The quenching rate constants of the visible emission of [Au 2(dcpm) 2] 2+ in acetonitrile by various anions are 6.08 × 10 5 (ClO 4 -), 9.18 × 10 5 (PF 6 -), 1.55 × 10 7 (Cl -) and 4.06 × 10 9 (I -) mol -1dm 3s -1. The triplet-state difference absorption spectra of 1-4 in acetonitrile show an absorption band with λ max at 350 nm and a shoulder/absorption maxima at 395-420 nm; their relative intensities are dependent upon the halide ion present in solution. Substrate binding reactions of the 3[dσ*pσ] excited state with halide (X -) to give [Au 2(dcpm) 2X] +* would account for the lower energy absorption maxima in the triplet-state difference absorption spectra. With iodide as the counterion, complex 7 undergoes a photoinduced electron-transfer reaction with I - to give the radical anion I 2 -. © Wiley-VCH Verlag GmbH, 2001. |
Persistent Identifier | http://hdl.handle.net/10722/167697 |
ISSN | 2023 Impact Factor: 3.9 2023 SCImago Journal Rankings: 1.058 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Fu, WF | en_US |
dc.contributor.author | Chan, KC | en_US |
dc.contributor.author | Cheung, KK | en_US |
dc.contributor.author | Che, CM | en_US |
dc.date.accessioned | 2012-10-08T03:10:10Z | - |
dc.date.available | 2012-10-08T03:10:10Z | - |
dc.date.issued | 2001 | en_US |
dc.identifier.citation | Chemistry - A European Journal, 2001, v. 7 n. 21, p. 4656-4664 | en_US |
dc.identifier.issn | 0947-6539 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167697 | - |
dc.description.abstract | The complexes [Au 2(dcpm) 2]-Y 2 (dcpm = bis(dicyclohexylphosphino)-methane; Y = ClO 4 - (1), PF 6 - (2), CF 3SO 3 - (3), Au(CN) 2 - (4), Cl - (5), SCN - (6) and I - (7)) were prepared, and the structures of 1 and 4-7 were determined by X-ray crystallography. Complexes 1-4 display intense phosphorescence with λ max at 360-368 nm in the solid state at room temperature as well as in glassy solutions at 77 K. The solid-state emission quantum yields of the powdered samples are 0.37 (1), 0.74 (2), 0.53 (3) and 0.12 (4). Crystalline solid 5 displays both high-energy UV (λ max = 366 nm) and low-energy visible emissions (λ max = 505 nm) at room temperature, whereas either 6 or 7 shows only an intense emission with λ max at 465 or 473 nm, respectively. All the complexes in degassed acetonitrile solutions exhibit an intense phosphorescence with λ max ranging from 490 to 530 nm. The high-energy UV emission is assigned to the intrinsic emission of the 3[dσ*pσ] excited state of [Au 2(dcpm) 2] 2+, whereas the visible emission is attributed to the adduct formation of the triplet excited state with the solvent/counterion. The quenching rate constants of the visible emission of [Au 2(dcpm) 2] 2+ in acetonitrile by various anions are 6.08 × 10 5 (ClO 4 -), 9.18 × 10 5 (PF 6 -), 1.55 × 10 7 (Cl -) and 4.06 × 10 9 (I -) mol -1dm 3s -1. The triplet-state difference absorption spectra of 1-4 in acetonitrile show an absorption band with λ max at 350 nm and a shoulder/absorption maxima at 395-420 nm; their relative intensities are dependent upon the halide ion present in solution. Substrate binding reactions of the 3[dσ*pσ] excited state with halide (X -) to give [Au 2(dcpm) 2X] +* would account for the lower energy absorption maxima in the triplet-state difference absorption spectra. With iodide as the counterion, complex 7 undergoes a photoinduced electron-transfer reaction with I - to give the radical anion I 2 -. © Wiley-VCH Verlag GmbH, 2001. | en_US |
dc.language | eng | en_US |
dc.publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry | en_US |
dc.relation.ispartof | Chemistry - A European Journal | en_US |
dc.subject | Binuclear Complexes | en_US |
dc.subject | Exciplexes | en_US |
dc.subject | Gold | en_US |
dc.subject | Luminescence | en_US |
dc.subject | Quenching | en_US |
dc.title | Substrate-binding reactions of the 3[dσ*pσ] excited state of binuclear gold(I) complexes with bridging bis(dicyclohexylphosphino)methane ligands: Emission and time-resolved absorption spectroscopic studies | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1002/1521-3765(20011105)7:21<4656::AID-CHEM4656>3.0.CO;2-D | - |
dc.identifier.pmid | 11757658 | - |
dc.identifier.scopus | eid_2-s2.0-0035813668 | en_US |
dc.identifier.hkuros | 72361 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0035813668&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 7 | en_US |
dc.identifier.issue | 21 | en_US |
dc.identifier.spage | 4656 | en_US |
dc.identifier.epage | 4664 | en_US |
dc.identifier.isi | WOS:000172133300015 | - |
dc.publisher.place | Germany | en_US |
dc.identifier.scopusauthorid | Fu, WF=7202947315 | en_US |
dc.identifier.scopusauthorid | Chan, KC=13609968400 | en_US |
dc.identifier.scopusauthorid | Cheung, KK=7402406613 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.issnl | 0947-6539 | - |