A ruthenium(II) tris(2,2′-bipyridine) derivative possessing a triplet lifetime of 42 μs

Harriman, Anthony; Hissler, Muriel; Khatyr, Abderrahim; Ziessel, Raymond

doi:10.1039/a900962k

Cited by 114 publications

(131 citation statements)

References 9 publications

Supporting

Mentioning

124

Contrasting

Order By: Relevance

“…[18] Recently, we developed a strategy to increase the triplet lifetime of luminescent ruthenium-poly(pyridine) complexes by attaching pyrene (pyr) fragments. [19,20] Pyrene, which is highly fluorescent, absorbs in a region of the spectral range where bodipy is essentially transparent and, as such, might make a useful light harvester. Furthermore, 1-ethynylpyrene appears to be a sufficiently versatile module to merit its attachment to a bodipy residue to form an interesting dualdye system with a conjugated connector.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Energy Transfer in Pyrene–Bodipy Molecular Dyads and Triads

Ziessel¹,

Goze²,

Ulrich³

et al. 2005

Chemistry A European J

Self Cite

173

140

View full text Add to dashboard Cite

Molecules bearing a 4,4-difluoro-8-(aryl)-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene (bodipy) core and 1-pyrenyl-1-phenyl-4-(1-ethynylpyrene), or 1-phenyl-4-[1-ethynyl-(6-ethynylpyrene)pyrene] units were constructed in a step-by-step procedure based on palladium(0)-promoted cross-coupling reactions with the required preconstructed modules. X-ray structures of single crystals reveal a twisted arrangement of the two chromophores. In one case, an almost perfect orthogonal arrangement is found. These dyes are strongly luminescent in solution and display rich electrochemistry in which all redox processes of the bodipy and pyrene fragments are clearly resolved. The absorption spectra indicate that the bodipy and pyrene chromophores are spectrally isolated, thereby inducing a large "virtual" Stokes shift. The latter is realised by efficient transfer of intramolecular excitation energy by the Förster dipole-dipole mechanism. The rate of energy transfer depends on the structure of the dual-dye system and decreases as the centre-to-centre separation increases. The energy transfer efficiency, however, exceeds 90 % in all cases. The linkage of two pyrene residues by an ethyne group leads to a decrease in the energy-transfer efficiency, with the two polycycles acting as a single chromophore. The directly linked bodipy-pyrene dual dye binds to DNA and operates as an efficient solar concentrator when dispersed in plastic.

show abstract

Section: Introductionmentioning

confidence: 99%

Intramolecular Energy Transfer in Pyrene–Bodipy Molecular Dyads and Triads

Ziessel¹,

Goze²,

Ulrich³

et al. 2005

Chemistry A European J

Self Cite

173

140

View full text Add to dashboard Cite

show abstract

“…At first glance, the results obtained with pyr ± Ru(terpy) appear disappointing in that the pyrene appendage provides little stabilization of the ªRu(terpy)º triplet state [44] because of the energy spacing. This is a false impression, however, since the triplet lifetime (t T 570 ns) observed for pyr ± Ru(terpy) greatly exceeds that recorded for any other ethynylated mononuclear ªRu(terpy)º fragment at room temperature, where t T values tend to be about 50 ns.…”

mentioning

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

Self Cite

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

“…Indeed, when four such units are connected through their nitrogen atoms to the pyrene backbone at positions 4, 5, 9 and 10, due to their localisation, each set of two pyrazolyl units on each side of the backbone will behave as a chelate, thus affording a bis-chelate tecton. Pyrene has previously been used as a backbone to anchor bipyridine, [12,13] terpyridine [13] and quinoline [14] units. Due to its planarity, pyrene 1 is poorly soluble in common solvents, and so we thought that the introduction of bulky and nonplanar tert-butyl substituents at positions 2 and 7, remote from the binding zones of the ligand, should overcome this insolubility problem.…”

Section: Resultsmentioning

confidence: 99%

Molecular Tectonics: Design of 1‐D Coordination Networks Based on Pyrene‐Bearing Pyrazolyl Units

2002

View full text Add to dashboard Cite

show abstract

A ruthenium(II) tris(2,2′-bipyridine) derivative possessing a triplet lifetime of 42 μs

Abstract: Grafting an ethynylated-pyrene moiety to a Ru(ii) or Os(ii) polypyridine complex perturbs the photophysical properties of the metal fragment and, when the relevant energy levels are properly balanced, provides a 115-fold prolongation of the triplet lifetime.

Cited by 114 publications

References 9 publications

Intramolecular Energy Transfer in Pyrene–Bodipy Molecular Dyads and Triads

Intramolecular Energy Transfer in Pyrene–Bodipy Molecular Dyads and Triads

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

Molecular Tectonics: Design of 1‐D Coordination Networks Based on Pyrene‐Bearing Pyrazolyl Units

Contact Info

Product

Resources

About