Intramolecular energy transfer in a chromophore-quencher complex

Boyde, Stephen; Strouse, Geoffroy F.; Jones, Wayne E.; Meyer, Thomas J.

doi:10.1021/ja00201a027

Cited by 76 publications

(52 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[5] In fact, several studies have described triplet energy transfer from a metal complex to an aryl hydrocarbon, [6±11] but in several cases the photosystems are unstable with respect to sensitized oxygenation of the polycycle. [6,7,9] Very recently, Schmehl and co-workers [12] studied the photophysical properties of ruthenium(ii) tris(diimine) complexes linked by a single bond to naphthalene or pyrene. It was concluded that the closely spaced terminals remained in weak electronic communication and that triplet states associated with these terminals were not in equilibrium at room temperature.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 1999

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

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

et al. 1999

View full text Add to dashboard Cite

show abstract

“…One of the possible processes occurring between dyes is excitation energy transfer, or "dipole-dipole long range interaction" (Forster, 1949). Fluorescence energy transfer is a powerful tool to determine the configuration of various molecules in solution or the respective location of fluorescent groups on a macromolecule because of its distance and orientation dependence (Albaugh and Steiner, 1989;Boyde et al, 1989;Cardullo el al., 1988;Morrisson et al, 1989;Murchie et al, 1989;Schiller, 1975). The large overlap between the fluorescence emission spectrum of 7R and the absorption spectrum of ethidium bromide makes them good candidates to investigate energy transfer processes.…”

Section: Introductionmentioning

confidence: 99%

FLUORESCENCE ENERGY TRANSFER BETWEEN DIMETHYLDIAZAPEROPYRENIUM DICATION AND ETHIDIUM INTERCALATED IN POLY d(A‐T)

Mergny

Slama‐Schwok

Montenay-Garestier

et al. 1991

Photochem & Photobiology

View full text Add to dashboard Cite

Dimethyldiazaperopyrenium is one of the largest known DNA intercalators. Fluorescence energy transfer occurred between dimethyldiazaperopyrenium (donor) and ethidium (acceptor) when these dyes were bound to a double-stranded polynucleotide such as poly d(A-T). The addition of increasing amounts of ethidium bromide led to a marked shortening of the fluorescence lifetime of the donor, whereas the excited state of the acceptor was progressively populated via energy transfer from the donor. Critical Förster distance between these two chromophores was calculated to be 3.8 nm. The observed transfer efficiency was lower than that calculated on the basis of this critical distance and a statistical distribution of bound drugs. These results are discussed taking into account the conformational change induced by intercalation of dimethyldiazaperopyrenium in the double-stranded polynucleotide.

show abstract

“…The compounds 4-[(9-anthrylmethoxy)methyl]-4′-methyl-2,2′-bipyridine (MebpyCH 2 OCH 2 An) 7 and [Re I (dmb)-(CO) 3 (4-Etpy)](PF 6 ) 8 were prepared and purified as described previously. [Re(dmb)-(CO) 3 (OTf)] (166 mg, 0.275 mmol; OTf is trifluoromethane sulfonate) and [MQ + ](PF 6 ) (96 mg, 0.32 mmol) were dissolved in ∼40 mL of CH 3 OH and heated at reflux for 3 h. After cooling, the solvent was removed under reduced pressure.…”

Section: Methodsmentioning

confidence: 99%

“…1-4 These include oxidative and reductive electron transfer quenching of metal-to-ligand charge transfer (MLCT) excited states, e.g., eq 1-2, 5,6 and energy transfer, eq 3, 7 These reactions can occur rapidly and with high efficiency.…”

Section: Introductionmentioning

confidence: 99%

Designed Intramolecular Competition in a Chromophore−Biquencher Complex

et al. 1996

Self Cite

View full text Add to dashboard Cite

Competitive energy and electron transfer occur following excitation of the chromophore-biquencher [Re I (MebpyCH 2 OCH 2 An)(CO) 3 (MQ + )](PF 6 ) 2 (MebpyCH 2 OCH 2 An is 4-[(9-anthrylmethoxy)methyl]-4′-methyl-2,2′-bipyridine; MQ + is N-methyl-4,4′,-bipyridinium ion). Following excitation with a 392-nm, 4-ns laser pulse in 1,2-dichloroethane (DCE), the initial excited state energy is distributed in a ∼2:1 ratio between 3 An* and the lower lying Re II (MQ ‚ ) metal-to-ligand charge transfer (MLCT) excited state. The appearance of the two states was monitored by transient absorption spectroscopy, which detected the triplet-triplet band for 3 An* at λ max ) 420 nm (τ ) 35 ( 2 µs, k ) (2.9 ( 0.2) × 10 4 s -1 ) and a π f π* band of MQ • at 610 nm (τ ) 37 ( 2 ns, k ) (2.7 ( 0.2) × 10 7 s -1 ). These states result from a competitive partitioning in the initial excited state or states. They do not interconvert to any significant degree on the time scale of the shorter lived, higher energy Re II (MQ*) state.

show abstract

Intramolecular energy transfer in a chromophore-quencher complex

Cited by 76 publications

References 6 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

FLUORESCENCE ENERGY TRANSFER BETWEEN DIMETHYLDIAZAPEROPYRENIUM DICATION AND ETHIDIUM INTERCALATED IN POLY d(A‐T)

Designed Intramolecular Competition in a Chromophore−Biquencher Complex

Contact Info

Product

Resources

About