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Article: Spectroscopic and excited-state properties of luminescent rhenium(I) N-heterocyclic carbene complexes containing aromatic diimine ligands

TitleSpectroscopic and excited-state properties of luminescent rhenium(I) N-heterocyclic carbene complexes containing aromatic diimine 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. 8, p. 1622-1630 How to Cite?
AbstractRhenium(I) N-heterocyclic carbene complexes of the type [HNCH 2CH 2NHCRe(L-L)(CO) 3] + have been prepared, where L-L = 4,4′-dimethoxy-2,2′-bipyridine (2), 4,4′-bis(tert-butyl)-2,2′-bipyridine (3), 2,2′-bipyridine (4), 4,4′-dichloro-2,2′-bipyridine (5), 4,4′-bis(carbomethoxy)-2,2′-bipyridine (6), 5-phenyl-1,10-phenanthroline (7), and o-phenylenebis(diphenylphosphine) (8). The molecular structures of 4, 6, and 8 have been determined by X-ray analyses and show Re-C(carbene) bond distances of 2.171(7), 2.163(4), and 2.199(6) Å, respectively. HF-SCF and MP 2 calculations on the model compound [HNCH 2CH 2NHCRe(NHCHCHNH)-(CO) 3] + (4m) show that the HOMO is nonbonding d(Re) and the LUMO is mainly π*(diimine) with partial p z(carbene) character. CIS calculations on the excited state of optimized 4m suggest that the lowest energy absorption originates from a HOMO to LUMO spin-forbidden transition. Complexes 2-7 are emissive at room temperature and 77 K. The room-temperature and 77 K luminescence data of 2-6 are consistent with emission from a 3-MLCT state. The nature of the emission of 7 at room temperature is also 3MLCT but changes to IL at 77 K. Complex 8 does not emit at room temperature, but at 77 K, the IL π(pdpp) → π(pdpp) emission is observed. The combination of detailed spectroscopic studies and theoretical calculations reveal that the emitting state at room temperature is 3[d(Re) → π*-(diimine)], with the latter exhibiting partial σ*(carbene) parentage. The excited-state energies and redox potentials can be tuned using diimine ligands with varying electron-donating/accepting abilities.
Persistent Identifierhttp://hdl.handle.net/10722/68888
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.authorChan, MCWen_HK
dc.contributor.authorSu, ZMen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorLiu, STen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:08:38Z-
dc.date.available2010-09-06T06:08:38Z-
dc.date.issued1998en_HK
dc.identifier.citationOrganometallics, 1998, v. 17 n. 8, p. 1622-1630en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/68888-
dc.description.abstractRhenium(I) N-heterocyclic carbene complexes of the type [HNCH 2CH 2NHCRe(L-L)(CO) 3] + have been prepared, where L-L = 4,4′-dimethoxy-2,2′-bipyridine (2), 4,4′-bis(tert-butyl)-2,2′-bipyridine (3), 2,2′-bipyridine (4), 4,4′-dichloro-2,2′-bipyridine (5), 4,4′-bis(carbomethoxy)-2,2′-bipyridine (6), 5-phenyl-1,10-phenanthroline (7), and o-phenylenebis(diphenylphosphine) (8). The molecular structures of 4, 6, and 8 have been determined by X-ray analyses and show Re-C(carbene) bond distances of 2.171(7), 2.163(4), and 2.199(6) Å, respectively. HF-SCF and MP 2 calculations on the model compound [HNCH 2CH 2NHCRe(NHCHCHNH)-(CO) 3] + (4m) show that the HOMO is nonbonding d(Re) and the LUMO is mainly π*(diimine) with partial p z(carbene) character. CIS calculations on the excited state of optimized 4m suggest that the lowest energy absorption originates from a HOMO to LUMO spin-forbidden transition. Complexes 2-7 are emissive at room temperature and 77 K. The room-temperature and 77 K luminescence data of 2-6 are consistent with emission from a 3-MLCT state. The nature of the emission of 7 at room temperature is also 3MLCT but changes to IL at 77 K. Complex 8 does not emit at room temperature, but at 77 K, the IL π(pdpp) → π(pdpp) emission is observed. The combination of detailed spectroscopic studies and theoretical calculations reveal that the emitting state at room temperature is 3[d(Re) → π*-(diimine)], with the latter exhibiting partial σ*(carbene) parentage. The excited-state energies and redox potentials can be tuned using diimine ligands with varying electron-donating/accepting abilities.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.titleSpectroscopic and excited-state properties of luminescent rhenium(I) N-heterocyclic carbene complexes containing aromatic diimine ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0276-7333&volume=17&issue=8&spage=1622&epage=1630&date=1998&atitle=Spectroscopic+and+excited-state+properties+of+luminescent+rhenium(I)+N-heterocyclic+carbene+complexes+containing+aromatic+diimine++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/om9709042-
dc.identifier.scopuseid_2-s2.0-0001447313en_HK
dc.identifier.hkuros32035en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0001447313&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume17en_HK
dc.identifier.issue8en_HK
dc.identifier.spage1622en_HK
dc.identifier.epage1630en_HK
dc.identifier.isiWOS:000073263600028-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridXue, WM=7103165059en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridSu, ZM=7402248791en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridLiu, ST=7409465977en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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