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Article: cis-dicyanoosmium(II) diimine complexes bearing phosphine or sulfoxide ligands: Spectroscopic and luminescent studies

Titlecis-dicyanoosmium(II) diimine complexes bearing phosphine or sulfoxide ligands: Spectroscopic and luminescent studies
Authors
Issue Date2007
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2007, v. 46 n. 26, p. 11003-11016 How to Cite?
AbstractA series of cis-dicyanoosmium(II) complexes [Os(PPh 3) 2(CN) 2(N∩N)] (N∩N = Ph 2phen (2a), bpy (2b), phen (2c), Ph 2bpy (2d), tBu 2bpy (2e)) and [Os(DMSO) 2(CN) 2(N∩N)] (3a-3e, N∩N = Br 2phen (31), Clphen (3g)), were synthesized and their spectroscopic and photophysical properties were examined, and [Os(PMe 3) 2(CN) 2(phen)] (4) with axial PMe 3 ligands was similarly prepared. The molecular structures of 2a, 2c, [2c·Zn(NO 3) 2] ∞, 2d, 2e, 3b, 3d, 3e, and 4 were determined by X-ray crystallographic analyses. The two CN ligands are cis to each other with mean Os-C bond distance of 2.0 Å. The two PR 3 (R = Ph, Me) or DMSO ligands are trans to each other with P/S-Os-P/S angles of ∼77°. The UV-vis absorption spectra of 2a-2e display an intense absorption band at 268-315 nm (ε = ∼(1.54-4.82) × 10 4 M -1 cm -1) that are attributed to π → π*(N∩N) and/or π → π*(PPH 3) transitions. The moderately intense absorption bands with λ max at 387-460 nm (ε = ∼ (2.4-11.3) × 10 3 M -1 cm -1) are attributed to a 1MLCT transition. A weak, broad absorption at 487-600 nm (ε = ∼390-1900 M -1 cm -1) is assigned to a 3MLCT transition. Excitation of 2a-2e in dichloromethane at 420 nm gives an emission with peak maximum at 654-703 nm and lifetime of 0.16-0.67 μs. The emission energies, lifetimes, and quantum yields show solvatochromic responses, and plots of ν max, τ, and Φ, respectively, versus E T (solvent polarity parameter) show linear correlations, indicating that the emission is sensitive to the local environment. The broad structureless solid-state emission of 2a-2e at 298 (λ max 622-707 nm) and 77 (λ max 602-675 nm) K are assigned to 3MLCT excited states. The 77 K MeOH/EtOH (1:4) glassy solutions of 2a-2e also exhibit 3MLCT emissions with λ max = 560-585 nm. The 1MLCT absorption and 3MLCT emission of 3a-3g occur at λ max = 332-390 nm and 553-644 nm, respectively. In the presence of Zn(NO 3) 2, both the 1MLCT absorption and 3MLCT emission of 2c in acetonitrile blue-shift from 397 to 341 nm and 651 to 531 nm, respectively. The enhancement of emission intensity (I/I o) of 2e at 531 nm reached a maximum of ∼810 upon the addition of two equivs of Zn(NO 3) 2. The crystallographic and spectroscopic evidence suggests that 2c undergoes binding of Zn 2+ ions via the cyano moieties. © 2007 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/70421
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, QKWen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:22:43Z-
dc.date.available2010-09-06T06:22:43Z-
dc.date.issued2007en_HK
dc.identifier.citationInorganic Chemistry, 2007, v. 46 n. 26, p. 11003-11016en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70421-
dc.description.abstractA series of cis-dicyanoosmium(II) complexes [Os(PPh 3) 2(CN) 2(N∩N)] (N∩N = Ph 2phen (2a), bpy (2b), phen (2c), Ph 2bpy (2d), tBu 2bpy (2e)) and [Os(DMSO) 2(CN) 2(N∩N)] (3a-3e, N∩N = Br 2phen (31), Clphen (3g)), were synthesized and their spectroscopic and photophysical properties were examined, and [Os(PMe 3) 2(CN) 2(phen)] (4) with axial PMe 3 ligands was similarly prepared. The molecular structures of 2a, 2c, [2c·Zn(NO 3) 2] ∞, 2d, 2e, 3b, 3d, 3e, and 4 were determined by X-ray crystallographic analyses. The two CN ligands are cis to each other with mean Os-C bond distance of 2.0 Å. The two PR 3 (R = Ph, Me) or DMSO ligands are trans to each other with P/S-Os-P/S angles of ∼77°. The UV-vis absorption spectra of 2a-2e display an intense absorption band at 268-315 nm (ε = ∼(1.54-4.82) × 10 4 M -1 cm -1) that are attributed to π → π*(N∩N) and/or π → π*(PPH 3) transitions. The moderately intense absorption bands with λ max at 387-460 nm (ε = ∼ (2.4-11.3) × 10 3 M -1 cm -1) are attributed to a 1MLCT transition. A weak, broad absorption at 487-600 nm (ε = ∼390-1900 M -1 cm -1) is assigned to a 3MLCT transition. Excitation of 2a-2e in dichloromethane at 420 nm gives an emission with peak maximum at 654-703 nm and lifetime of 0.16-0.67 μs. The emission energies, lifetimes, and quantum yields show solvatochromic responses, and plots of ν max, τ, and Φ, respectively, versus E T (solvent polarity parameter) show linear correlations, indicating that the emission is sensitive to the local environment. The broad structureless solid-state emission of 2a-2e at 298 (λ max 622-707 nm) and 77 (λ max 602-675 nm) K are assigned to 3MLCT excited states. The 77 K MeOH/EtOH (1:4) glassy solutions of 2a-2e also exhibit 3MLCT emissions with λ max = 560-585 nm. The 1MLCT absorption and 3MLCT emission of 3a-3g occur at λ max = 332-390 nm and 553-644 nm, respectively. In the presence of Zn(NO 3) 2, both the 1MLCT absorption and 3MLCT emission of 2c in acetonitrile blue-shift from 397 to 341 nm and 651 to 531 nm, respectively. The enhancement of emission intensity (I/I o) of 2e at 531 nm reached a maximum of ∼810 upon the addition of two equivs of Zn(NO 3) 2. The crystallographic and spectroscopic evidence suggests that 2c undergoes binding of Zn 2+ ions via the cyano moieties. © 2007 American Chemical Society.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.titlecis-dicyanoosmium(II) diimine complexes bearing phosphine or sulfoxide ligands: Spectroscopic and luminescent studiesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=46&spage=11003&epage=11016&date=2007&atitle=cis-Dicyanoosmium(II)+Diimine+Complexes+Bearing+Phosphine+or+Sulfoxide+Ligands:+Spectroscopic+and+Luminescent+Studiesen_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic070290len_HK
dc.identifier.pmid18031033-
dc.identifier.scopuseid_2-s2.0-38149009035en_HK
dc.identifier.hkuros139809en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-38149009035&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume46en_HK
dc.identifier.issue26en_HK
dc.identifier.spage11003en_HK
dc.identifier.epage11016en_HK
dc.identifier.isiWOS:000251773700015-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLai, SW=55104882100en_HK
dc.identifier.scopusauthoridChan, QKW=14041210100en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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