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• W2531530279 endingPage "11184" @default.
• W2531530279 startingPage "11170" @default.
• W2531530279 abstract "A series of Ru(II) 2,2'-bipyridine (bpy) complexes with an electron-accepting dipyrido[3,2-a:2',3'-c]phenazine (dppz) ligand coupled to an electron-donating triarylamine (TAA) group have been investigated. Systematic alteration of a bridging unit between the dppz and TAA allowed exploration into how communication between the donor and acceptor is perturbed by distance, as well as by steric and electronic effects. The effect of the bridging group on the electronic properties of the systems was characterized using a variety of spectroscopic methods, including Fourier transform-Raman (FT-Raman) spectroscopy, resonance Raman spectroscopy, and transient resonance Raman (TR2) spectroscopy. These methods were used in conjunction with ground- and excited-state absorption spectroscopy, electrochemical studies, and DFT calculations. The ground-state electronic absorption spectra show distinct variation with the bridging group, with the wavelength observed for the lowest energy electronic transition ranging from 449 nm to 522 nm, accompanied by large changes in the molar absorptivity. The lowest-energy Franck-Condon state was determined to be intra-ligand charge transfer (ILCT) in nature for most compounds. The presence of higher-energy metal-to-ligand charge transfer (MLCT) Ru(II) → bpy and Ru(II) → dppz transitions was also confirmed via resonance Raman spectroscopy. The TR2 spectra showed characteristic dppz• - and TAA• + vibrations, indicating that the THEXI state formed was also ILCT in nature. Excited-state lifetime measurements reveal that the rate of decay is in accordance with the energy gap law and is not otherwise affected by the nature of the bridging unit." @default.
• W2531530279 created "2016-10-21" @default.
• W2531530279 creator A5001016791 @default.
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• W2531530279 creator A5030147314 @default.
• W2531530279 creator A5075147918 @default.
• W2531530279 creator A5083995578 @default.
• W2531530279 date "2016-10-10" @default.
• W2531530279 modified "2023-09-24" @default.
• W2531530279 title "Effect of Bridge Alteration on Ground- and Excited-State Properties of Ruthenium(II) Complexes with Electron-Donor-Substituted Dipyrido[3,2-<i>a</i>:2′,3′-<i>c</i>]phenazine Ligands" @default.
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• W2531530279 doi "https://doi.org/10.1021/acs.inorgchem.6b01810" @default.
• W2531530279 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/27723325" @default.
• W2531530279 hasPublicationYear "2016" @default.
• W2531530279 type Work @default.
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