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• W4385334191 endingPage "12885" @default.
• W4385334191 startingPage "12872" @default.
• W4385334191 abstract "With the goal of developing a new strategy for the synthesis of luminescent Ru(II) complexes, we have prepared herein a new set of bis-tridentate complexes of the type [(py-bpy-Ph-X)Ru(tpy-PhCH3)]ClO4 (X = −CH3, −CH2Br, and −CHO) incorporating both non-cyclometalated and cyclometalated coordination motifs of two isomeric forms of methylphenyl-terpyridine (tpy-PhCH3). Thorough characterization of the synthesized complexes is carried out using standard analytical tools and single crystal X-ray diffraction. Detailed investigations on their photophysical and electrochemical behaviors are carried out in MeCN. The presence of a carbanionic center in the cyclometalating unit increases the absorption spectral window of the complexes into a longer-wavelength region. The complexes also exhibit room-temperature luminescence in the NIR domain with enhanced excited-state lifetimes (up to 20.1 ns) compared to their non-cyclometalated counterpart, [Ru(tpy-PhCH3)2]2+. In the presence of acid, the non-coordinated nitrogen atom in the secondary coordination sphere of the complexes allows fine-tuning of the absorption and emission spectral properties. Excess acid induces de-coordination of the Ru–C bond, which is signaled by a remarkable alteration of their spectral profiles. Cleavage of the Ru–C bond is also possible upon treating the acidified solution of the complexes with visible light. Restoration of the Ru–C bond is again feasible upon treating the solution with base at an elevated temperature (∼70 °C). In essence, “on–off” and “off–on” switching of emission is facilitated upon alternating treatment of the Ru(II) complexes with acid, base, and temperature. DFT and TD-DFT calculations are also performed for assignments of the spectral bands as well as to understand structural changes associated with the switching behaviors of the complexes." @default.
• W4385334191 created "2023-07-29" @default.
• W4385334191 creator A5003482591 @default.
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• W4385334191 date "2023-07-28" @default.
• W4385334191 modified "2023-09-24" @default.
• W4385334191 title "Influences of Both N,N,N- and N,N,C-Coordination Modes of Tolyl-terpyridine on the Photophysical Properties of Cyclometalated Ru(II) Complexes: Combined Experimental and Theoretical Investigations on Acid/Base-Dependent Reversible Cyclometalation" @default.
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• W4385334191 doi "https://doi.org/10.1021/acs.inorgchem.3c01523" @default.
• W4385334191 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/37506326" @default.
• W4385334191 hasPublicationYear "2023" @default.
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