Primary charge separation in photoinduced multielectron storage systems. A dinuclear ruthenium(<scp>ii</scp>) species featuring a charge-separated state with a lifetime of 1.3 µs

Chiorboli, Claudio; Fracasso, Sandro; Scandola, Franco; Campagna, Sebastiano; Serroni, Scolastica; Konduri, Rama; MacDonnell, Frederick M.

doi:10.1039/b302962j

Cited by 37 publications

(25 citation statements)

References 22 publications

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“…Ultrafast spectroscopic investigations of RuRu indicated that the MLCT should be localized on the phenanthroline-like sphere of the tatpp ligand. 9 The resonance Raman spectrum of RuRu should, therefore, be very similar to Ruphen. The second potential explanation, i.e.…”

Section: Resultsmentioning

confidence: 99%

Resonance Raman studies of photochemical molecular devices for multielectron storage

Tschierlei

Dietzek

Karnahl

et al. 2008

J Raman Spectroscopy

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Section: Resultsmentioning

confidence: 99%

Resonance Raman studies of photochemical molecular devices for multielectron storage

Tschierlei

Dietzek

Karnahl

et al. 2008

J Raman Spectroscopy

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“…[55][56][57][58][59] Within one of these systems, a long-lived CS state of about 1.3 ms could be obtained. [16] Also, very recently, Fukuzumi and co-workers [60] succeeded in reaching hundreds of ms timescale for CS lifetimes within a dyad based on weakly coupled Zn-porphyrin (P/D) and C 60 (A) as well as in a purely organic bipartite molecule build up of mesityl (P/D) and methyl-acridinium (A) moieties. However, in spite of these recent advances towards ultra long-lived CS states, still the very detailed working mode of these compact dyads has to be elucidate.…”

Section: General Commentsmentioning

confidence: 99%

“…[16] Expectedly, the intercomponent electronic coupling can be modulated via a controlled intramolecular conformation, [17][18][19] by simply changing the torsion angle (0 q 1 908, Figure 1) between the P and A parts of the potentially fully conjugated molecule P-(q 1 )-A. The only parameter to be varied is then the actual degree of electronic conjugation of A with P. In this context, the photophysical properties of the 0-bpy-2-bpy series of complexes are compared with those of an affiliated species (1-phen) previously described by Hupp and co-workers.…”

Section: Introductionmentioning

confidence: 97%

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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“…For artificial photosynthesis, multi‐electron redox chemistry and the accumulation of oxidative and reductive equivalents are highly relevant. [1] Light‐driven charge accumulation in molecular compounds is readily possible with sacrificial electron donors or acceptors,[2] but ultimately the use of such energy‐rich reagents is undesirable . Consequently, it seems important to explore the fundamentals of light‐driven charge accumulation.…”

Section: Introductionmentioning

confidence: 99%

Pump‐Pump‐Probe Spectroscopy of a Molecular Triad Monitoring Detrimental Processes for Photoinduced Charge Accumulation

Kuss‐Petermann

Wenger

2016

Helvetica Chimica Acta

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Controlling light-induced accumulation of electrons or holes is desirable in view of multi-electron redox chemistry, for example for the formation of solar fuels or for photoredox catalysis in general. Excitation with multiple photons is usually required for electron or hole accumulation, and consequently pump-pump-probe spectroscopy becomes a valuable spectroscopic tool. In this work, we excited a triarylamine-Ru(bpy)3 2+ -anthraquinone triad (bpy = 2,2'-bipyridine) with two temporally delayed laser pulses of different color and monitored the resulting photoproducts. Absorption of the first photon by the Ru(bpy)3 2+ photosensitizer generated a triarylamine radical cation and an anthraquinone radical anion by intramolecular electron transfer. Subsequent selective excitation of either one of these two radical ion species then induced rapid reverse electron transfer to yield the triad in its initial (ground) state. This shows in direct manner that after absorption of a first photon and formation of the primary photoproducts, the absorption of a second photon can lead to unproductive electron transfer events that counteract further charge accumulation. In principle, this problem is avoidable by careful excitation wavelength selection in combination with good molecular design.

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Primary charge separation in photoinduced multielectron storage systems. A dinuclear ruthenium(ii) species featuring a charge-separated state with a lifetime of 1.3 µs

Cited by 37 publications

References 22 publications

Resonance Raman studies of photochemical molecular devices for multielectron storage

Resonance Raman studies of photochemical molecular devices for multielectron storage

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

Pump‐Pump‐Probe Spectroscopy of a Molecular Triad Monitoring Detrimental Processes for Photoinduced Charge Accumulation

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