Reversible triplet-triplet energy transfer within a covalently linked bichromophoric molecule

Ford, William E.; Rodgers, Michael A. J.

doi:10.1021/j100186a026

Cited by 212 publications

(255 citation statements)

References 4 publications

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“…There is a modest variation in the size of the electron ± vibrational coupling constants. While pyr ± Os gives an S value similar to that found for the parent complex [Os(bpy) 3 ] 2 (S 0.69) [10] the value found for pyr ± Pt ± Os is larger. This parameter is related to the nuclear displacement between ground and triplet states [28] so that the central Pt unit increases structural differences between triplet and ground states.…”

Section: Introductionsupporting

confidence: 70%

“…[17] Comparison with the triplet energy calculated for the parent complex [Os(bpy) 3 ] 2 (E T 14 700 cm À1 ) [10] shows that the substituent has almost no effect on the triplet energy of pyr ± Pt ± Os, perhaps raising it by about 100 cm…”

Section: Introductionmentioning

confidence: 99%

“…[3±12] Thus, Ford and Rodgers [3] observed reversible triplet energy transfer between a ruthenium(ii) tris(polypyridine) complex and a covalently linked pyrene moiety. Equilibration between the two triplet states localized on the terminals of this highly flexible dyad extended the phosphorescence lifetime of the metal complex from about 1 ms to 11.2 ms in deoxygenated solution at room temperature.…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular Triplet Energy Transfer in Pyrene-Metal Polypyridine Dyads: A Strategy for Extending the Triplet Lifetime of the Metal Complex

et al. 1999

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A series of photoactive dyads bearing pyrene and metal (M Ru II ) or Os II ) tris(2,2'-bipyridine) terminals bridged by an ethynylene or Pt II bis(sacetylide) moiety has been synthesized and investigated by transient spectroscopy. Selective excitation into the terminal metal complex is possible in each case and generates the lowest energy, excited triplet state localized on that molecular fragment. For both Os II -based dyads, the triplet state is unperturbed by the appended pyrene unit and the observed photophysical properties can be understood within the framework of the energy-gap law. The triplet state localized on the metal complex in the two Ru II -based dyads is involved in reversible energy transfer with the triplet associated with the pyrene unit, which is situated at slightly lower energy. When the terminal metal complex is a Ru II bis(2,2':6',2''-terpyridyl) fragment, however, the triplet levels are inverted such that the pyrene-like triplet state lies slightly above that of the metal complex. Kinetic spectrophotometry has allowed determination of the various rate constants and energy gaps and, on the basis of nonadiabatic electron-transfer theory, it appears that the central Pt bis(sacetylide) unit is a much inferior electronic conductor than is a simple ethynylene group. Reversible energy transfer of this type greatly prolongs the triplet lifetime of the Ru II tris(2,2'-bipyridyl) fragment. For example, equilibration between the triplet states is achieved within 10 ps for the ethynylenebridged dyad while the equilibrium mixture decays with a lifetime of about 40 ms in deoxygenated acetonitrile at room temperature.

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Section: Introductionsupporting

confidence: 70%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Intramolecular Triplet Energy Transfer in Pyrene-Metal Polypyridine Dyads: A Strategy for Extending the Triplet Lifetime of the Metal Complex

et al. 1999

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“…compound of the thermal equilibrium [31]. These derived lifetimes can be used to determine the fraction (α) of triplet MLCT present at equilibrium (table 1) and it is seen that this is a relatively high value.…”

Section: Photophysical Properties Of the Homotopic Metal Complexesmentioning

confidence: 99%

Providing power for miniaturized medical implants: triplet sensitization of semiconductor surfaces

Benniston

Harriman

Yang

2013

Phil. Trans. R. Soc. A.

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Here, we recognize the growing significance of miniaturized devices as medical diagnostic tools and highlight the need to provide a convenient means of powering such instruments when implanted into the body. One of the most promising approaches to this end involves using a light-collection facility to absorb incident white light and transfer the photonic energy to a tiny semiconductor embedded on the device. Although fluorescent organic molecules offer strong potential as modules for such solar collectors, we emphasize the promise offered by transition metal complexes. Thus, an extended series of binuclear Ru(II)/Os(II) poly(pyridine) complexes has been shown to be highly promising sensitizers for amorphous silicon solar cells. These materials absorb a high fraction of visible light while the Ru(II)-based units possess triplet energies that are comparable to those of the naphthalene-based bridge. The metal complex injects a triplet exciton into the bridge and this, in turn, is trapped by the Os(II)-based terminal. The result is extremely efficacious triplet-energy transfer; at room temperature the rate of energy transfer is independent of distance over some 6 nm and only weakly dependent on temperature.

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“…[15]. A thermal triplet equilibrium has been suggested in this phenomenon [10,16]. The long-lived 3 MLCT excited state of the Ru complex enables decay time measurements in biomedical applications [17] and allows one to free oneself from tissue autofluorescence (which typically decays within several nanoseconds, and thus does not interfere with the detection of the emission of the ruthenium complexes at longer times).…”

Section: Excited-state Lifetime Engineering In Ru(ii) Polypyridyl Commentioning

confidence: 99%

3MLCT excited states in Ru(II) complexes: Reactivity and related two-photon absorption applications in the near-infrared spectral range

Lemercier

Bonne

Four

et al. 2008

Comptes Rendus. Chimie

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This short review provides a concise summary of the current state of research on the population by two-photon absorption of the triplet metal-to-ligand RésuméCette courte revue a pour objectif de fournir un état de l'art actuel, le plus concis et précis possible, concernant la recherche sur le phénomène de population par absorption à deux photons de l'état excité triplet à transfert de charge 3 MLTC au sein de complexes du ruthénium(II). Outre les applications de ce phénomène d'optique non linéaire à la limitation optique dans le proche infrarouge, des applications plus particulières en biologie (imagerie, dosage tant in vitro que in vivo du dioxygène et thérapie photodynamique ou PDT) sont ici décrites et envisagées. Pour citer cet article : G. Lemercier et al., C. R. Chimie 11 (2008).

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Reversible triplet-triplet energy transfer within a covalently linked bichromophoric molecule

Cited by 212 publications

References 4 publications

Intramolecular Triplet Energy Transfer in Pyrene-Metal Polypyridine Dyads: A Strategy for Extending the Triplet Lifetime of the Metal Complex

Intramolecular Triplet Energy Transfer in Pyrene-Metal Polypyridine Dyads: A Strategy for Extending the Triplet Lifetime of the Metal Complex

Providing power for miniaturized medical implants: triplet sensitization of semiconductor surfaces

3MLCT excited states in Ru(II) complexes: Reactivity and related two-photon absorption applications in the near-infrared spectral range

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