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Article: Bis(tridentate) Iron(II) Complexes with a Cyclometalating Unit: Photophysical Property Enhancement with Combinatorial Strong Ligand Field Effect

TitleBis(tridentate) Iron(II) Complexes with a Cyclometalating Unit: Photophysical Property Enhancement with Combinatorial Strong Ligand Field Effect
Authors
Issue Date2020
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2020, v. 39 n. 15, p. 2791-2802 How to Cite?
AbstractA series of bis(tridentate) cyclometalated oligopyridine complexes [FeII(C∧N∧N)(L)]+ have been synthesized via the reactions of [FeII(C∧Npy∧Npy)Br(PMe3)2] (1, HC∧Npy∧Npy = 6-(phenyl)-2,2′-bipyridine) and [FeII(C∧Nppy∧Nisoquin)Br(PMe3)2] (2, HC∧Nppy∧Nisoquin = 3-(4,6-diphenylpyridin-2-yl)isoquinoline) with tridentate ligands L, affording [FeII(C∧Npy∧Npy)(4′-R-tpy)]+ (3a–e, R = H, Cl, p-ClC6H4, p-MeOC6H4, p-tol, respectively; tpy = 2,2′:6′,2″-terpyridine), [FeII(C∧Nppy∧Nisoquin)(tpy)]+ (4), [FeII(C∧Npy∧Npy)(6-(Ph2PCH2)-bpy)]+ (5, bpy = 2,2′-bipyridine), and [FeII(C∧Npy∧Npy)(6-NHC-bpy)]+ (6, NHC = N-heterocyclic carbene). Complexes 3–6 exhibit bathochromically shifted absorption bands, markedly cathodically shifted E1/2(FeIII/FeII) values, and narrowed electrochemical band gaps in comparison to those of [FeII(tpy)2]2+, as revealed by UV–vis absorption spectroscopy and cyclic voltammetry. DFT and TDDFT calculation studies revealed strong mixing of MLCT with LLCT transitions as origins to the major absorption bands. Complex 6 incorporating a cyclometalating unit and an NHC donor exhibits panchromic absorption, and 5 shows markedly enhanced molar absorptivity in the visible region. A femtosecond transient absorption spectroscopic study of 6, coupled with DFT and TDDFT calculations and spectroelectrochemical measurements, gave evidence for the possible involvement of a 3MLCT state with a lifetime of 21.4 ps.
Persistent Identifierhttp://hdl.handle.net/10722/286621
ISSN
2023 Impact Factor: 2.5
2023 SCImago Journal Rankings: 0.654
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorTang, Z-
dc.contributor.authorChang, XY-
dc.contributor.authorWan, Q-
dc.contributor.authorWang, J-
dc.contributor.authorMa, C-
dc.contributor.authorLaw, KC-
dc.contributor.authorLiu, Y-
dc.contributor.authorChe, CM-
dc.date.accessioned2020-09-04T13:28:10Z-
dc.date.available2020-09-04T13:28:10Z-
dc.date.issued2020-
dc.identifier.citationOrganometallics, 2020, v. 39 n. 15, p. 2791-2802-
dc.identifier.issn0276-7333-
dc.identifier.urihttp://hdl.handle.net/10722/286621-
dc.description.abstractA series of bis(tridentate) cyclometalated oligopyridine complexes [FeII(C∧N∧N)(L)]+ have been synthesized via the reactions of [FeII(C∧Npy∧Npy)Br(PMe3)2] (1, HC∧Npy∧Npy = 6-(phenyl)-2,2′-bipyridine) and [FeII(C∧Nppy∧Nisoquin)Br(PMe3)2] (2, HC∧Nppy∧Nisoquin = 3-(4,6-diphenylpyridin-2-yl)isoquinoline) with tridentate ligands L, affording [FeII(C∧Npy∧Npy)(4′-R-tpy)]+ (3a–e, R = H, Cl, p-ClC6H4, p-MeOC6H4, p-tol, respectively; tpy = 2,2′:6′,2″-terpyridine), [FeII(C∧Nppy∧Nisoquin)(tpy)]+ (4), [FeII(C∧Npy∧Npy)(6-(Ph2PCH2)-bpy)]+ (5, bpy = 2,2′-bipyridine), and [FeII(C∧Npy∧Npy)(6-NHC-bpy)]+ (6, NHC = N-heterocyclic carbene). Complexes 3–6 exhibit bathochromically shifted absorption bands, markedly cathodically shifted E1/2(FeIII/FeII) values, and narrowed electrochemical band gaps in comparison to those of [FeII(tpy)2]2+, as revealed by UV–vis absorption spectroscopy and cyclic voltammetry. DFT and TDDFT calculation studies revealed strong mixing of MLCT with LLCT transitions as origins to the major absorption bands. Complex 6 incorporating a cyclometalating unit and an NHC donor exhibits panchromic absorption, and 5 shows markedly enhanced molar absorptivity in the visible region. A femtosecond transient absorption spectroscopic study of 6, coupled with DFT and TDDFT calculations and spectroelectrochemical measurements, gave evidence for the possible involvement of a 3MLCT state with a lifetime of 21.4 ps.-
dc.languageeng-
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics-
dc.relation.ispartofOrganometallics-
dc.titleBis(tridentate) Iron(II) Complexes with a Cyclometalating Unit: Photophysical Property Enhancement with Combinatorial Strong Ligand Field Effect-
dc.typeArticle-
dc.identifier.emailTang, Z: zhoutang@hku.hk-
dc.identifier.emailWan, Q: wendyqyw@hku.hk-
dc.identifier.emailChe, CM: chemhead@hku.hk-
dc.identifier.authorityChe, CM=rp00670-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/acs.organomet.0c00149-
dc.identifier.scopuseid_2-s2.0-85088577554-
dc.identifier.hkuros314020-
dc.identifier.volume39-
dc.identifier.issue15-
dc.identifier.spage2791-
dc.identifier.epage2802-
dc.identifier.isiWOS:000562124400002-
dc.publisher.placeUnited States-
dc.identifier.issnl0276-7333-

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