Influence Of Electronic Delocalization In Metal-to-Ligand Charge Transfer Excited States

Strouse, Geoffrey F.; Schoonover, Jon R.; Duesing, Richard; Boyde, Stephen; Jones, Wayne E. Jr.; Meyer, Thomas J.

doi:10.1021/ic00106a009

Cited by 248 publications

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“…25 An analogous change in structure is believed to occur upon reduction of biphenyl; 26 a similar Femtosecond Absorption Spectroscopy McCusker delocalization effect had previously been invoked by Meyer and co-workers to explain anomalously long excitedstate lifetimes in certain binuclear Ru II complexes. 27 The extended π system of the coplanar state would also increase the magnitude of effective charge separation and lead to a larger transition dipole, thereby increasing k r . Additional data in support of this model included nanosecond time-resolved resonance Raman spectra.…”

Section: If There Is No Change In the Spectral Profile Of The Transiementioning

confidence: 99%

Femtosecond Absorption Spectroscopy of Transition Metal Charge‐Transfer Complexes

McCusker

2004

ChemInform

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Our research is concerned with the application of femtosecond time-resolved absorption techniques to the study of the photophysics of transition metal complexes. The focus is to understand the events that characterize the process of excited-state evolution from the time a photon is absorbed by a molecule to the formation of the lowest-energy excited state of the system. This Account describes our initial observations in this area and includes examples detailing these dynamics as they occur in the charge-transfer excited states of transition-metal polypyridyl chromophores.

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Section: If There Is No Change In the Spectral Profile Of The Transiementioning

confidence: 99%

Femtosecond Absorption Spectroscopy of Transition Metal Charge‐Transfer Complexes

McCusker

2004

ChemInform

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“…In the latter case, the conformational change is anticipated to result in an increase of the electron-accepting strength of A, [17d, 44] thus lowering the energy of the CS state-once formed-within *[1-bpy] and amplifying the electron delocalization within MLCT" level attached to the phen-pyridinium "superligand") [45] remains hitherto unclear (Figure 8). …”

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confidence: 99%

Photoinduced Processes within Compact Dyads Based on Triphenylpyridinium‐Functionalized Bipyridyl Complexes of Ruthenium(II)

Lainé

Ciofini

Ochsenbein

et al. 2005

Chemistry A European J

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As an alternative to conventional charge-separation functional molecular models based on long-range ET within redox cascades, a "compact approach" has been examined. To this end, spacer elements usually inserted between main redox-active units within polyad systems have been removed, allowing extended rigidity but at the expense of enhanced intercomponent electronic communication. The molecular assemblies investigated here are of the P-(theta (1))-A type, where the theta (1) twist angle is related to the degree of conjugation between the photosensitizer (P, of {Ru(bpy)(3)}(2+) type) and the electron-acceptor (A). 4-N- and 4-N-,4'-N-(2,4,6-triphenylpyridinio)-2,2'-bipyridine ligands (A(1)-bpy and A(2)-bpy, respectively) have been synthesized to give complexes with Ru(II), 1-bpy and 2-bpy, respectively. Combined solid-state analysis (X-ray crystallography), solution studies ((1)H NMR, cyclic voltammetry) and computational structural optimization allowed verifying that theta (1) angle approaches 90 degrees within 1-bpy and 2-bpy in solution. Also, anticipated existence of strong intercomponent electronic coupling has been confirmed by investigating electronic absorption properties and electrochemical behavior of the compounds. The capability of 1-bpy and 2-bpy to undergo PET process was evaluated by carrying out their photophysical study (steady state emission and time-resolved spectroscopy at both 293 and 77 K). The conformational dependence of photoinduced processes within P-(theta (1))-A systems has been established by comparing the photophysical properties of 1-bpy (and 2-bpy) with those of an affiliated species reported in the literature, 1-phen. A complementary theoretical analysis (DFT) of the change of spin density distribution within model [1-bpy(theta (1))](-) mono-reduced species as a function of theta (1) has been undertaken and the possibility of conformationally switching emission properties of P was derived.

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“…Triphenylphosphonium salt of 4-(bromomethyl)-4'-methyl-2,2'-bipyridine was prepared according to the literature. [26][27][28] Zinc 5,10,15,20-tetra-ptolylporphyrin (ZnTTP) was prepared by addition of zinc acetate to dichloromethane solution of 5,10,15,20-tetra-ptolylporphyrin (TTP). Spectroscopic and electrochemical measurements.…”

Section: Methodsmentioning

confidence: 99%

Noncovalently Linked Zinc Porphyrin-Ru(bpy)₃Dyad Assembled via Axial Coordination

2003

Bulletin of the Korean Chemical Society

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Noncovalently linked electron donor-acceptor dyad consisting of zinc tetratolylporphyrin and pyridineappended ruthenium trisbipyridine complex was prepared, via axial coordination of pyridine moiety in ruthenium trisbipyridine complex on zinc tetratolylporphyrin. For the purpose of comparison, axial coordination of pyridine-appended 2,2'-bipyridine on zinc tetratolylporphyrin was also investigated. The K values were determined based on absorption or fluorescence studies. The fluorescence of zinc tetratolylporphyrin was efficiently quenched upon axial coordination of pyridine moiety, probably due to the photoinduced electron transfer from zinc tetratolylporphyrin to ruthenium trisbipyridine, supported by free energy estimation.

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Influence Of Electronic Delocalization In Metal-to-Ligand Charge Transfer Excited States

Cited by 248 publications

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Femtosecond Absorption Spectroscopy of Transition Metal Charge‐Transfer Complexes

Femtosecond Absorption Spectroscopy of Transition Metal Charge‐Transfer Complexes

Photoinduced Processes within Compact Dyads Based on Triphenylpyridinium‐Functionalized Bipyridyl Complexes of Ruthenium(II)

Noncovalently Linked Zinc Porphyrin-Ru(bpy)₃Dyad Assembled via Axial Coordination

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Influence Of Electronic Delocalization In Metal-to-Ligand Charge Transfer Excited States

Cited by 248 publications

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Femtosecond Absorption Spectroscopy of Transition Metal Charge‐Transfer Complexes

Femtosecond Absorption Spectroscopy of Transition Metal Charge‐Transfer Complexes

Photoinduced Processes within Compact Dyads Based on Triphenylpyridinium‐Functionalized Bipyridyl Complexes of Ruthenium(II)

Noncovalently Linked Zinc Porphyrin-Ru(bpy)3Dyad Assembled via Axial Coordination

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Noncovalently Linked Zinc Porphyrin-Ru(bpy)₃Dyad Assembled via Axial Coordination