Singlet and triplet energy transfer processes in ruthenium(II) bipyridine complexes containing covalently bound arenes

Wilson, Gerard J.; Sasse, W. H. F.; Mau, Albert W. H.

doi:10.1016/0009-2614(96)00056-5

Cited by 72 publications

(46 citation statements)

References 24 publications

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“…This result was partially attributed to uorescence resonance energy transfer (FRET) occurring from the polymer backbones to the iTMC units via the 1 MLCT excited state and is consistent with literature examples when the donor emission and acceptor absorption spectral signatures overlap. 16,20,21 Furthermore, in the excitation spectra of the hybrid polymers monitored for the Ru(II) 3 MLCT emission at 640 nm (Fig. 2B), the conjugated main-chain absorption spectra could be in part reproduced, in agreement with FRET.…”

Section: Photophysical Propertiessupporting

confidence: 52%

Poly(fluorene-co-thiophene)-based ionic transition-metal complex polymers for solar energy harvesting and storage applications

et al. 2014

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This paper describes the synthesis, electrochemical and photophysical properties of two poly(fluorene-cothiophene)-based polymers featuring pendant Ru(II) polypyridyl-based ionic transition metal complexes.These systems combine long-lived excited states of the Ru(II) chromophores and the large optical crosssections of the conjugated backbones, potentially allowing for polymer-assisted solar radiationharvesting and storage functions via ultrafast energy and charge transfer processes. Modified azidealkyne "click" cycloaddition chemistry conditions are demonstrated as an effective approach to obtain quantitatively functionalized conjugated polymer-ionic transition metal complex assemblies.Introduction of variable fractions of electron-rich thiophene units into these architectures induces a bathochromic shift in the polyfluorene absorption maxima, while simultaneously stabilizing the oxidized states of the conjugated scaffolds, as determined by electrochemical and in situ spectroelectrochemical experiments. The hybrid assemblies exhibit ultrafast energy flow (700 fs to 4.8 ps) and photoinduced charge-separation (1.8-2.0 ps) between the conjugated backbone and the Ru(II) moieties. Notably, the chemical composition of the main-chain repeat unit determines the dominant pathway for decay of the conjugated backbone excited states with the fraction of electron transfer increasing from 25% to 75% upon incorporation of an additional thiophene heterocycle.

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Section: Photophysical Propertiessupporting

confidence: 52%

Poly(fluorene-co-thiophene)-based ionic transition-metal complex polymers for solar energy harvesting and storage applications

et al. 2014

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“…Undertaking an alternative approach, − we herein report the development of a series of new bichromophoric triplet PS with ultralong triplet lifetimes of a few milliseconds but still exhibiting decent phosphorescence quantum yields (Φ up to 0.64). Specifically, the bichromophoric scaffold comprises an organic chromophore pyrene covalently linked to a triscyclometalated iridium complex (Chart ).…”

Section: Introductionmentioning

confidence: 99%

Iridium-Based High-Sensitivity Oxygen Sensors and Photosensitizers with Ultralong Triplet Lifetimes

Jiang

Wang

et al. 2015

ACS Appl. Mater. Interfaces

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The photophysics of a series of bichromophoric molecules featuring an intramolecular triplet energy transfer between a triscyclometalated iridium(III) complex and covalently linked organic group are studied. By systematically varying the energy gap (0.1-0.3 eV) between the donor (metal complex) and acceptor (pyrene unit), reversible triplet energy transfer processes with equilibrium constant K ranging from ca. 500 to 40 000 are established. Unique photophysical consequences of such large K values are observed. Because of the highly imbalanced forward and backward energy transfer rates, triplet excitons dominantly populate the acceptor moiety in the steady state, giving rise to ultralong luminescence lifetimes up to 1-4 ms. Because the triscyclometalated Ir and triplet pyrene groups both impart relatively small nonradiative energy loss, decent phosphorescence quantum yields (Φ = 0.1-0.6) are attained in spite of the exceptionally prolonged excited states. By virtue of such precious combination of long-lived triplet state and high Φ, these bichromophoric molecules can serve as highly sensitive luminescent sensors for detecting trace amount of O2 and as potent photosensitizers for producing singlet oxygen even under low-oxygen content conditions.

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“…A longer luminescence lifetime of 2.5 ms for L2:Ru (Table 1) MLCT and a fluorene triplet state are in a rapid equilibrium. [13] However, enhanced ESA properties are obtained in LT2:Ru complexes with an extinction coefficient e ESA of 9500 m ), as a function of the laser wavelength in comparison with s TPA variations (Figures 6 a and b respectively), allows the analysis of OPL data. The spectral dispersion of Th and T 10 shows the best efficiency at any wavelength of the complex LT2:Ru, for which both parameters are significantly weaker (Table 2).…”

mentioning

confidence: 97%

Ruthenium(II) Complexes for Two‐Photon Absorption‐Based Optical Power Limiting

et al. 2008

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International audienceLong-lived excitation: Novel bifluorene-substituted 1,10-phenanthroline-based RuII coordination complexes are presented (see picture). They fulfil several requirements for optimized optical power limiting in the visible-NIR, as they are stable, soluble and transparent at low laser fluences. The two-photon absorption of these complexes are strongly related to those of the ligand

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Singlet and triplet energy transfer processes in ruthenium(II) bipyridine complexes containing covalently bound arenes

Cited by 72 publications

References 24 publications

Poly(fluorene-co-thiophene)-based ionic transition-metal complex polymers for solar energy harvesting and storage applications

Poly(fluorene-co-thiophene)-based ionic transition-metal complex polymers for solar energy harvesting and storage applications

Iridium-Based High-Sensitivity Oxygen Sensors and Photosensitizers with Ultralong Triplet Lifetimes

Ruthenium(II) Complexes for Two‐Photon Absorption‐Based Optical Power Limiting

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