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• W2314361674 endingPage "9896" @default.
• W2314361674 startingPage "9885" @default.
• W2314361674 abstract "Ruthenium(II) and osmium(II) complexes [M(C^N^C)(N^N)L]n+ (L = Cl–, n = 1; L = CH3CN, t-BuNC, n = 2) containing a neutral tridentate N-heterocyclic carbene (NHC)-based pincer ligand, either 2,6-bis(1-butylimidazol-2-ylidene)pyridine (C1^N^C1) or 2,6-bis(3-butylbenzimidazol-2-ylidene)pyridine (C2^N^C2), and a neutral 2,2′-bipyridine-type aromatic diimine have been prepared. Investigations into the effects of varying M (Ru and Os), C^N^C, N^N, and L on the structural, electrochemical, absorption, and emission characteristics associated with [M(C^N^C)(N^N)L]n+ are presented. Interestingly, spectroscopic findings and time-dependent density functional theory (TD-DFT) calculations in this work support a dπ(RuII/OsII) → π*(N^N) metal-to-ligand charge transfer (MLCT) assignment for the lowest-energy transition in [M(C^N^C)(N^N)L]n+ and not a dπ(RuII/OsII) → π*(C^N^C) MLCT assignment. This is in stark contrast to [Ru(tpy)(bpy)Cl]+ and [Os(tpy)(bpy)Cl]+ (tpy = 2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine) for which the lowest-energy transitions are assigned as dπ(Ru/Os) → π*(tpy) MLCT transitions. [RuII(C^N^C)(N^N)L]n+ is emissive with emission maxima of around 600–700 nm observed upon photoexcitation of their dπ(RuII) → π*(N^N) MLCT bands. The electronic structures for [Ru(C^N^C)(N^N)Cl]0 have also been probed by spectroelectrochemistry, electron paramagnetic resonance (EPR) spectroscopy, and DFT calculations, which reveal that the lowest unoccupied molecular orbitals (LUMOs) for [Ru(C^N^C)(N^N)Cl]+ are N^N-based." @default.
• W2314361674 created "2016-06-24" @default.
• W2314361674 creator A5027199528 @default.
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• W2314361674 creator A5073896912 @default.
• W2314361674 creator A5074734961 @default.
• W2314361674 creator A5083643595 @default.
• W2314361674 date "2013-08-16" @default.
• W2314361674 modified "2023-09-26" @default.
• W2314361674 title "Ruthenium(II) and Osmium(II) Complexes Bearing Bipyridine and the N-Heterocyclic Carbene-Based C^N^C Pincer Ligand: An Experimental and Density Functional Theory Study" @default.
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• W2314361674 doi "https://doi.org/10.1021/ic4010196" @default.
• W2314361674 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/23952294" @default.
• W2314361674 hasPublicationYear "2013" @default.
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