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Article: Cyclometalated Iron and Ruthenium Complexes Supported by a Tetradentate Ligand Scaffold with Mixed O, N, and C Donor Atoms: Synthesis, Structures, and Excited-State Properties
Title | Cyclometalated Iron and Ruthenium Complexes Supported by a Tetradentate Ligand Scaffold with Mixed O, N, and C Donor Atoms: Synthesis, Structures, and Excited-State Properties |
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Authors | |
Issue Date | 2022 |
Citation | Organometallics, 2022, v. 41, n. 4, p. 418-429 How to Cite? |
Abstract | A series of cyclometalated Fe(II/III) and Ru(II/III) complexes bearing a tetradentate dianionic [O^N^C^N] ligand (H2[O^N^C^N] = 2-(6-(3-(pyridin-2-yl)phenyl)pyridin-2-yl)phenol) was synthesized and structurally characterized. The strong-field dianionic [O^N^C^N] ligand enforces all of these complexes in a low-spin state at 298 K as revealed by 1H NMR, magnetic susceptibility, and electron paramagnetic resonance (EPR) measurements. A 77 K 2-MeTHF (THF = tetrahydrofuran) glassy solution of the bis(2,6-dimethylphenyl isocyanide) Ru(II) complex [RuII(O^N^C^N)(XylNC)2] displays a weak and broad emission band (λem: 680 nm; τ: 0.27 μs), while the others are nonemissive. Density functional theory (DFT)/time-dependent DFT calculations revealed that 1dd excited states of the d6 [MII(O^N^C^N)(PMe3)2] (M = Fe, Ru) are strongly destabilized. The [FeII(O^N^C^N)(PMe3)2] exhibits panchromatic absorption up to 850 nm. A combined study of femtosecond transient absorption (fs-TA), spectro-electrochemistry, and theoretical calculation revealed that the possible triplet metal-to-ligand charge transfer (3MLCT) excited state (τ: 14 ps) of [FeII(O^N^C^N)(PMe3)2] decays via a lower-lying 3dd excited state. For the d5 [MIII(O^N^C^N)(PMe3)2]+ (M = Fe, Ru), the presence of low-lying 2dd excited states and doublet ligand-to-metal charge transfer (2LMCT) states with short lifetimes (τ: 11.7-12.6 ps) is suggested. |
Persistent Identifier | http://hdl.handle.net/10722/314017 |
ISSN | 2023 Impact Factor: 2.5 2023 SCImago Journal Rankings: 0.654 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Law, Kwok Chung | - |
dc.contributor.author | Tang, Zhou | - |
dc.contributor.author | Wu, Liangliang | - |
dc.contributor.author | Wan, Qingyun | - |
dc.contributor.author | To, Wai Pong | - |
dc.contributor.author | Chang, Xiaoyong | - |
dc.contributor.author | Low, Kam Hung | - |
dc.contributor.author | Liu, Yungen | - |
dc.contributor.author | Che, Chi Ming | - |
dc.date.accessioned | 2022-07-06T11:28:52Z | - |
dc.date.available | 2022-07-06T11:28:52Z | - |
dc.date.issued | 2022 | - |
dc.identifier.citation | Organometallics, 2022, v. 41, n. 4, p. 418-429 | - |
dc.identifier.issn | 0276-7333 | - |
dc.identifier.uri | http://hdl.handle.net/10722/314017 | - |
dc.description.abstract | A series of cyclometalated Fe(II/III) and Ru(II/III) complexes bearing a tetradentate dianionic [O^N^C^N] ligand (H2[O^N^C^N] = 2-(6-(3-(pyridin-2-yl)phenyl)pyridin-2-yl)phenol) was synthesized and structurally characterized. The strong-field dianionic [O^N^C^N] ligand enforces all of these complexes in a low-spin state at 298 K as revealed by 1H NMR, magnetic susceptibility, and electron paramagnetic resonance (EPR) measurements. A 77 K 2-MeTHF (THF = tetrahydrofuran) glassy solution of the bis(2,6-dimethylphenyl isocyanide) Ru(II) complex [RuII(O^N^C^N)(XylNC)2] displays a weak and broad emission band (λem: 680 nm; τ: 0.27 μs), while the others are nonemissive. Density functional theory (DFT)/time-dependent DFT calculations revealed that 1dd excited states of the d6 [MII(O^N^C^N)(PMe3)2] (M = Fe, Ru) are strongly destabilized. The [FeII(O^N^C^N)(PMe3)2] exhibits panchromatic absorption up to 850 nm. A combined study of femtosecond transient absorption (fs-TA), spectro-electrochemistry, and theoretical calculation revealed that the possible triplet metal-to-ligand charge transfer (3MLCT) excited state (τ: 14 ps) of [FeII(O^N^C^N)(PMe3)2] decays via a lower-lying 3dd excited state. For the d5 [MIII(O^N^C^N)(PMe3)2]+ (M = Fe, Ru), the presence of low-lying 2dd excited states and doublet ligand-to-metal charge transfer (2LMCT) states with short lifetimes (τ: 11.7-12.6 ps) is suggested. | - |
dc.language | eng | - |
dc.relation.ispartof | Organometallics | - |
dc.title | Cyclometalated Iron and Ruthenium Complexes Supported by a Tetradentate Ligand Scaffold with Mixed O, N, and C Donor Atoms: Synthesis, Structures, and Excited-State Properties | - |
dc.type | Article | - |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1021/acs.organomet.1c00677 | - |
dc.identifier.scopus | eid_2-s2.0-85124905176 | - |
dc.identifier.volume | 41 | - |
dc.identifier.issue | 4 | - |
dc.identifier.spage | 418 | - |
dc.identifier.epage | 429 | - |
dc.identifier.eissn | 1520-6041 | - |
dc.identifier.isi | WOS:000767339100006 | - |