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Article: Luminescent nitridoosmium(VI) complexes with aryl- and alkylacetylide ligands: Spectroscopic properties and crystal structures

TitleLuminescent nitridoosmium(VI) complexes with aryl- and alkylacetylide ligands: Spectroscopic properties and crystal structures
Authors
Issue Date2003
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2003, v. 22 n. 2, p. 315-320 How to Cite?
AbstractA series of air- and moisture-stable nitridoosmium(VI) complexes with arylacetylide ligands, [ nBu 4N][OsN(C≡CC 6H 4R-p) 4 ] (R = H (1), Et (2), OEt (3), Ph (4)), and the alkyl analogue [ nBu 4N] [OsN(C≡C tBu) 4] (5) were synthesized. The structures of 1, 2, and 4 were determined by X-ray crystal analyses. The Os≡N (1.65(1) Å in 1, 1.620(8) Å in 2, and 1.619(6) Å in 4) and Os-C (mean 2.03 Å) distances are similar to that observed for [OsN(CH 2SiMe 3) 4] -, whereas the C≡C distances (mean 1.20 Å) correspond to terminal arylacetylide groups. The UV-vis absorption spectra of 1-4 display intense absorptions at 248-324 nm (ε ≈ 5 × 10 4 dm 3 mol -1 cm -1) that are attributed to overlapping of the [p π*(N 3-) → d π*(d xz, d yz)] and [π → π*(arylacetylides)] transitions. The moderately intense absorptions at λ max 403-418 nm (ε ≈ 10 3 dm 3 mol -1 cm -1) are assigned to admixture of [(d xy) 2 → (d xy) 1(d π*) 1] with intraligand charge-transfer transition of the arylacetylides. The broad structureless solid-state luminescence of 1-5 at 298 (λ max 600-632 nm) and 77 K (λ max 599-635 nm) are assigned to the triplet 3[(d xy) 1(d π*) 1] excited state. The 77 K glassy solutions of 1-5 also exhibit 3[(d xy) 1(d π*) 1] emissions at λ max 597-628 nm. Like [OsNX 4] - (X = Cl, Br), complexes 1-5 are nonemissive in dichloromethane at room temperature. Notably, 1 emits weakly at λ max 643 nm in benzene at room temperature, whereas 5 exhibits a more intense and long-lived luminescence at λ max 640 nm in diethyl ether. Correspondingly, a well-defined absorption at λ max 428 nm in the excitation spectrum of 5 (λ em 640 nm, concentration 8 × 10 -4 mol dm -3) is assigned to the 1[(d xy) 2] → 1[(d xy) 1(d π*) 1] transition.
Persistent Identifierhttp://hdl.handle.net/10722/70392
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLai, SWen_HK
dc.contributor.authorLau, TCen_HK
dc.contributor.authorFung, WKMen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:22:27Z-
dc.date.available2010-09-06T06:22:27Z-
dc.date.issued2003en_HK
dc.identifier.citationOrganometallics, 2003, v. 22 n. 2, p. 315-320en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70392-
dc.description.abstractA series of air- and moisture-stable nitridoosmium(VI) complexes with arylacetylide ligands, [ nBu 4N][OsN(C≡CC 6H 4R-p) 4 ] (R = H (1), Et (2), OEt (3), Ph (4)), and the alkyl analogue [ nBu 4N] [OsN(C≡C tBu) 4] (5) were synthesized. The structures of 1, 2, and 4 were determined by X-ray crystal analyses. The Os≡N (1.65(1) Å in 1, 1.620(8) Å in 2, and 1.619(6) Å in 4) and Os-C (mean 2.03 Å) distances are similar to that observed for [OsN(CH 2SiMe 3) 4] -, whereas the C≡C distances (mean 1.20 Å) correspond to terminal arylacetylide groups. The UV-vis absorption spectra of 1-4 display intense absorptions at 248-324 nm (ε ≈ 5 × 10 4 dm 3 mol -1 cm -1) that are attributed to overlapping of the [p π*(N 3-) → d π*(d xz, d yz)] and [π → π*(arylacetylides)] transitions. The moderately intense absorptions at λ max 403-418 nm (ε ≈ 10 3 dm 3 mol -1 cm -1) are assigned to admixture of [(d xy) 2 → (d xy) 1(d π*) 1] with intraligand charge-transfer transition of the arylacetylides. The broad structureless solid-state luminescence of 1-5 at 298 (λ max 600-632 nm) and 77 K (λ max 599-635 nm) are assigned to the triplet 3[(d xy) 1(d π*) 1] excited state. The 77 K glassy solutions of 1-5 also exhibit 3[(d xy) 1(d π*) 1] emissions at λ max 597-628 nm. Like [OsNX 4] - (X = Cl, Br), complexes 1-5 are nonemissive in dichloromethane at room temperature. Notably, 1 emits weakly at λ max 643 nm in benzene at room temperature, whereas 5 exhibits a more intense and long-lived luminescence at λ max 640 nm in diethyl ether. Correspondingly, a well-defined absorption at λ max 428 nm in the excitation spectrum of 5 (λ em 640 nm, concentration 8 × 10 -4 mol dm -3) is assigned to the 1[(d xy) 2] → 1[(d xy) 1(d π*) 1] transition.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_HK
dc.relation.ispartofOrganometallicsen_HK
dc.titleLuminescent nitridoosmium(VI) complexes with aryl- and alkylacetylide ligands: Spectroscopic properties and crystal structuresen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0276-7333&volume=22&spage=315&epage=320&date=2003&atitle=Luminescent+nitridoosmium(VI)+complexes+with+aryl-+and+alkylacetylide+ligands:+spectroscopic+properties+and+crystal+structuresen_HK
dc.identifier.emailLai, SW: swlai@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityLai, SW=rp00717en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/om0206204en_HK
dc.identifier.scopuseid_2-s2.0-0037455550en_HK
dc.identifier.hkuros80439en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037455550&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume22en_HK
dc.identifier.issue2en_HK
dc.identifier.spage315en_HK
dc.identifier.epage320en_HK
dc.identifier.isiWOS:000180408900013-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLai, SW=7402937200en_HK
dc.identifier.scopusauthoridLau, TC=7102222310en_HK
dc.identifier.scopusauthoridFung, WKM=37062711800en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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