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Article: Tuning the excited-state properties of luminescent rhenium(V) benzylidyne complexes containing phosphorus and nitrogen donor ligands

TitleTuning the excited-state properties of luminescent rhenium(V) benzylidyne complexes containing phosphorus and nitrogen donor ligands
Authors
Issue Date1998
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 1998, v. 17 n. 10, p. 1946-1955 How to Cite?
AbstractEfficient methods are developed for the synthesis of rhenium(V)-substituted benzylidyne complexes with various auxiliary ligands to facilitate the tuning of their excited-state properties. The electronic structures and spectroscopic and photophysical properties of [Re(≡CAr′)(pdpp)2Cl] + (Ar′ = C 6H 2Me 3-2,4,6, pdpp = o-phenylenebis(diphenylphosphine), 2), [Re(≡CAr′)L 2(CO)(H 2O)Cl] + (L = PPh 3, 3; P(C 6H 4OMe-p) 3, 4; PPh 2Me, 5), [Re(≡CAr′)(dppe)-(CO) 2Cl] + (dppe = 1,2-bis(diphenylphosphino)ethane, 6), [Re(≡CAr′)(L-L)(CO) 2Cl] + (L-L = 2,2′-bipyridine, 7; 4,4′-dichloro-2,2′-bipyridine, 8; 4,4′-dimethoxycarbonyl-2,2′-bipyridine, 9), [Re(≡CAr′)(TpO(CO) 2] + (Tp′ = tris(3,5-dimethyl-1-pyrazolyl)borohydride, 10), and [Re(≡CC 6H 4-R)(pdPp)(CO) 2(O 3SCF 3)] + (13, R = OMe, a; Me, b; H, c; Cl, d; Br, e; CN, f) are studied and compared. The molecular structures of 7·CHCl 3, 10, 12f, 13a·CH 3OH·H 2O, and 13d·2CH 2Cl 2 are determined by X-ray crystallography and reveal Re≡C distances in the 1.766(8)-1.786(7) Å range. HF-SCF calculations on the model compounds [Re(≡CC 6H 5)(H 2-PCH=CHPH 2) 2C1] + (2m), [Re(≡CC 6H 5)(PH 3) 2(H 2O)(CO)Cl] + (3m), and [Re(≡CC 6H 5)(H 2-PCH=CHPH 2)(CO) 2(OH)] + (13m) suggest that the HOMO is π(Re≡C-Ph) and the LUMO is ¶*(Re=C-Ph). CI-singles calculations on the excited state of optimized 2m indicate that the lowest energy UV-vis absorption of 2-6, 10, and 13 originates from a HOMO to LUMO spin-forbidden transition. This is identified as 3[π(Re≡CAr) → π* (Re≡CAr)], where d(Re) → p(≡C) MLCT character is apparent and the p(≡C) orbital and phenyl π system are conjugated. The UV-vis absorption spectra of 7-9 are significantly different, and their lowest energy absorption is assigned d(Re) → π*(X 2-bpy). The rhenium(V) benzylidyne complexes are highly emissive at room temperature and 77 K. The combination of spectroscopic studies and theoretical calculations suggest that the emitting state of 2-6, 10, and 13 is 3[π(Re≡CAr)→π*(Re=CAr)] but that of 7-9 is d(Re) →*(X 2-bpy). The emission energies in dichloromethane can be adjusted from 520 to 610 nm by variation of the benzylidyne and ancillary ligands. Their electrochemical behaviors are examined and provide further evidence to support the excited-state assignment.
Persistent Identifierhttp://hdl.handle.net/10722/70034
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorXue, WMen_HK
dc.contributor.authorWang, Yen_HK
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorSu, ZMen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:19:05Z-
dc.date.available2010-09-06T06:19:05Z-
dc.date.issued1998en_HK
dc.identifier.citationOrganometallics, 1998, v. 17 n. 10, p. 1946-1955en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70034-
dc.description.abstractEfficient methods are developed for the synthesis of rhenium(V)-substituted benzylidyne complexes with various auxiliary ligands to facilitate the tuning of their excited-state properties. The electronic structures and spectroscopic and photophysical properties of [Re(≡CAr′)(pdpp)2Cl] + (Ar′ = C 6H 2Me 3-2,4,6, pdpp = o-phenylenebis(diphenylphosphine), 2), [Re(≡CAr′)L 2(CO)(H 2O)Cl] + (L = PPh 3, 3; P(C 6H 4OMe-p) 3, 4; PPh 2Me, 5), [Re(≡CAr′)(dppe)-(CO) 2Cl] + (dppe = 1,2-bis(diphenylphosphino)ethane, 6), [Re(≡CAr′)(L-L)(CO) 2Cl] + (L-L = 2,2′-bipyridine, 7; 4,4′-dichloro-2,2′-bipyridine, 8; 4,4′-dimethoxycarbonyl-2,2′-bipyridine, 9), [Re(≡CAr′)(TpO(CO) 2] + (Tp′ = tris(3,5-dimethyl-1-pyrazolyl)borohydride, 10), and [Re(≡CC 6H 4-R)(pdPp)(CO) 2(O 3SCF 3)] + (13, R = OMe, a; Me, b; H, c; Cl, d; Br, e; CN, f) are studied and compared. The molecular structures of 7·CHCl 3, 10, 12f, 13a·CH 3OH·H 2O, and 13d·2CH 2Cl 2 are determined by X-ray crystallography and reveal Re≡C distances in the 1.766(8)-1.786(7) Å range. HF-SCF calculations on the model compounds [Re(≡CC 6H 5)(H 2-PCH=CHPH 2) 2C1] + (2m), [Re(≡CC 6H 5)(PH 3) 2(H 2O)(CO)Cl] + (3m), and [Re(≡CC 6H 5)(H 2-PCH=CHPH 2)(CO) 2(OH)] + (13m) suggest that the HOMO is π(Re≡C-Ph) and the LUMO is ¶*(Re=C-Ph). CI-singles calculations on the excited state of optimized 2m indicate that the lowest energy UV-vis absorption of 2-6, 10, and 13 originates from a HOMO to LUMO spin-forbidden transition. This is identified as 3[π(Re≡CAr) → π* (Re≡CAr)], where d(Re) → p(≡C) MLCT character is apparent and the p(≡C) orbital and phenyl π system are conjugated. The UV-vis absorption spectra of 7-9 are significantly different, and their lowest energy absorption is assigned d(Re) → π*(X 2-bpy). The rhenium(V) benzylidyne complexes are highly emissive at room temperature and 77 K. The combination of spectroscopic studies and theoretical calculations suggest that the emitting state of 2-6, 10, and 13 is 3[π(Re≡CAr)→π*(Re=CAr)] but that of 7-9 is d(Re) →*(X 2-bpy). The emission energies in dichloromethane can be adjusted from 520 to 610 nm by variation of the benzylidyne and ancillary ligands. Their electrochemical behaviors are examined and provide further evidence to support the excited-state assignment.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.titleTuning the excited-state properties of luminescent rhenium(V) benzylidyne complexes containing phosphorus and nitrogen donor ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0276-7333&volume=17&spage=1946&epage=1955&date=1998&atitle=Tuning+the+excited-state+properties+of+luminescent+rhenium(V)+benzylidyne+complexes+containing+phosphorus+and+nitrogen+donor+ligandsen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/om971054t-
dc.identifier.scopuseid_2-s2.0-0000653026en_HK
dc.identifier.hkuros32048en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0000653026&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume17en_HK
dc.identifier.issue10en_HK
dc.identifier.spage1946en_HK
dc.identifier.epage1955en_HK
dc.identifier.isiWOS:000073789900013-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridXue, WM=7103165059en_HK
dc.identifier.scopusauthoridWang, Y=8637619000en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridSu, ZM=7402248791en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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