Excited-State Structure and Delocalization in Ruthenium(II)−Bipyridine Complexes That Contain Phenyleneethynylene Substituents

Wang, Yingsheng; Liu, Shengxia; Pinto, Maurício R.; Dattelbaum, Dana M.; Schoonover, and Jon R.; Schanze, Kirk S.

doi:10.1021/jp013008j

Cited by 56 publications

(49 citation statements)

References 55 publications

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“…Second, it can cause an electronic structure in which a ligand-centered (LC) excited state localized on the extended π-system becomes important for the overall photophysics. The first scenario is commonly referred to as the delocalization effect, 35,36,[39][40][41][42][43][44][45] and the latter is often referred to as the triplet reservoir effect. 37,38,[46][47][48] Which one of these two effects dominates is largely dependent on whether there is substantial electronic coupling between the metal core and the extended π-system, or whether these two parts are electronically decoupled from one another.…”

Section: Discussionmentioning

confidence: 99%

Luminescent chromium(0) and manganese(i) complexes

Wegeberg

Wenger

2022

Dalton Trans.

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Section: Discussionmentioning

confidence: 99%

Luminescent chromium(0) and manganese(i) complexes

Wegeberg

Wenger

2022

Dalton Trans.

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“…Experimentally it has, however, been observed that functionalization of [Ru(bpy) 3 ] 2+ with different OPE rigid rods influences the experimental absorption spectra significantly in the visible region. 49,22 Here, we present TD-DFT calculated absorption spectra to provide detailed theoretical information concern-ing the nature of the different excitations. TD-DFT spectra of [Ru(bpy) 3 ] 2+ and 1-3 in acetonitrile are presented in Figure 3a, and experimental absorption spectra in acetonitrile are shown in Figure 3b.…”

Section: (A) Influence Of Rod Length and Conjugation On Opticalmentioning

confidence: 99%

Calculated Optoelectronic Properties of Ruthenium Tris-bipyridine Dyes Containing Oligophenyleneethynylene Rigid Rod Linkers in Different Chemical Environments

et al. 2007

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Ruthenium tris-bipyridine dyes containing oligophenyleneethynylene (OPE) rigid rod linker groups ([Ru(bpy)3]2+, [Ru(bpy)2bpy-E-Ipa]2+, [Ru(bpy)2bpy-E-Ph-E-Ipa]2+, and [Ru(bpy)2bpy-E-Bco-E-Ipa]2+, where bpy = 2,2'-bipyridine, E = ethynylene, Ph = p-phenylene, Bco = bicyclo[2.2.2]octylene, and Ipa = isophthalic acid) have been investigated using DFT and TD-DFT calculations to elucidate the influence of the rigid rod on their optoelectronic properties. Experimentally observed differences in the optical absorption for the different complexes are discussed on the basis of TD-DFT simulated absorption spectra. A comparison of the calculated optoelectronic properties of [Ru(bpy)2bpy-E-Ph-E-Ipa]2+ in different chemical environments, that is, in different solvents and with or without counter ions, suggests that both the absorption spectra and the redox properties of the dyes with OPE rods are sensitive to the environment. The calculations show that spurious low-energy charge-transfer excitations present in the TD-DFT calculations of the extended systems in vacuum are removed when the environment is included in the calculations.

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“…[16][17][18] One area of particular interest in our work involves platinum acetylides. 19,20 This class of materials exhibits optical properties that are similar to oligo-and poly(phenylene ethynylene)s, 21 which can be thought of as the all-organic analogues of platinum acetylide oligomers and polymers.…”

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Photophysics and Photochemistry of Stilbene-Containing Platinum Acetylides

et al. 2004

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A series of four platinum acetylide complexes that contain 4-ethynylstilbene (4-ES) ligands have been subjected to a detailed photochemical and photophysical investigation. The objective of the work is to understand the structure and reactivity of the lowest excited states in π-conjugated Pt-acetylides. The 4-ES ligand was chosen for this work because the excited-state properties of the stilbene chromophore are well understood. In particular, stilbene features fluorescence and phosphorescence, and also undergoes trans-cis photoisomerization from the triplet excited state. Two of the complexes investigated contain phosphine ligands and have the structures trans-Pt(PBu 3 ) 2 (4-ES) 2 and cis-Pt(dppe)(4-ES) 2 (2 and 3, respectively, where PBu 3 ) tributylphosphine and dppe ) bis-1,2-diphosphinoethane). The other two complexes contain substituted 2,2′-bipyridine ligands and have the structures Pt(t-Bu-bpy)(4-ES) 2 and Pt(4,4′-CO 2 Et-bpy)(4-ES) 2 (3 and 4, respectively, where t-Bubpy ) 4,4′-di-tert-butyl-2,2′-bipyridine and 4,4′-CO 2 Et-bpy ) 4,4′-bis(carboethoxy)-2,2′-bipyridine). The crystal structure of 2 is reported. The complex features a square planar PtP 2 C 2 geometry and the planes of the phenyl groups in the 4-ES ligands are twisted approximately 60°relative to the plane defined by the PtP 2 C 2 core. The series of complexes was examined by using absorption, variable-temperature photoluminescence, and transient absorption spectroscopy. In addition, the photochemical reactivity of the complexes was explored by UV-visible absorption and NMR spectroscopy. The available experimental data indicate that in all of the complexes excitation leads to high-yield production of a 3 π,π* excited state that is localized on one of the 4-ES ligands. At low temperatures, the 3 π,π* state exhibits strong phosphorescence that is very similar to the phosphorescence of trans-stilbene. At temperatures above the glass-to-fluid temperature of the solvent medium, the 3 π,π* state decays rapidly (τ ≈ 40 ns). The decay pathway is believed to involve rotation around the CdC bond of one of the 4-ES moieties. This model is supported by the photochemical results, which show that steady-state photolysis leads to trans-cis isomerization of one of the 4-ES ligands with a quantum efficiency of 0.4.

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Excited-State Structure and Delocalization in Ruthenium(II)−Bipyridine Complexes That Contain Phenyleneethynylene Substituents

Cited by 56 publications

References 55 publications

Luminescent chromium(0) and manganese(i) complexes

Luminescent chromium(0) and manganese(i) complexes

Calculated Optoelectronic Properties of Ruthenium Tris-bipyridine Dyes Containing Oligophenyleneethynylene Rigid Rod Linkers in Different Chemical Environments

Photophysics and Photochemistry of Stilbene-Containing Platinum Acetylides

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