Synthetic control of excited states. Nonchromophoric ligand variations in polypyridyl complexes of osmium(II)

Kober, Edward M.; Marshall, Janet L.; Dressick, Walter J.; Sullivan, B. Patrick; Caspar, Jonathan V.; Meyer, Thomas J.

doi:10.1021/ic00212a010

Cited by 183 publications

(141 citation statements)

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“…The solutions were deaerated by Ar purging for at least 20 min prior to measurement. The quantum yields were determined by comparison to [(bpy) 3 Ru] 2ϩ in acetonitrile solution (Φ ϭ 0.062), [61] and were found to be generally lower by the factor of 100 or more compared to this standard. Time-resolved emission spectra of samples in 2-MeTHF glasses (90 K) were recorded in an Oxford Instruments cryostat, using Spectra Physics GCR3 Nd:YAG or Coherent Infinity XPO lasers as excitation sources and an OMA detection system described elsewhere.…”

Section: Instrumentationmentioning

confidence: 99%

Co‐Ligand Involvement in Ground and Excited States of Electron‐Rich (Polypyridyl)Pt^II Complexes

2003

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were determined from single-crystal XRD and discussed in view of intermolecular interactions that influence the emission behaviour. The combination of theoretical calculations (DFT) and spectroscopic techniques (absorption and emission) revealed the character of electronic transitions and excited states. In particular they showed that the co-ligand involvement in the frontier orbitals is small for R = Me, but large in case of R = alkynyl, Ph or Mes. Depending on the chelate ligand and its substitution

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Section: Instrumentationmentioning

confidence: 99%

Co‐Ligand Involvement in Ground and Excited States of Electron‐Rich (Polypyridyl)Pt^II Complexes

2003

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“…Emission maxima were reproducible to within AE 5 nm. Quantum yields were calculated relative to ruthenium(ii) and osmium(ii) tris(2,2'-bipyridyl) complexes in acetonitrile [29,56] with dilute solutions after deoxygenation by purging with argon. Luminescence quantum yields were taken as the average of three separate determinations and were reproducible to within AE 8 % but, because of the low emission probability for the…”

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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

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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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“…This valued chemical stability allows one designing bis-and even tris-heteroleptic compounds [81]. Various approaches aiming at manipulating the properties of MLCT excited states (and especially the lifetime of T 1 ) are well documented [77,[82][83][84][85][86][87][88][89]. They can be categorized into coarse-tuning those modifications concerning the core of P (that is, P0; Fig.…”

Section: 42 Below)mentioning

confidence: 99%

“…P0 bpy ) or a poor (e.g. P0 tpy ) luminophore, the red-shifted emission of the derived P1 series of photosensitizers obtained by the decoration of P0 will be respectively more [30,88,89,103] or less [84] sensitive to energy gap law.…”

Section: Coarse-and Fine-tuning Of Excited-state Properties Of Ru(ii)mentioning

confidence: 99%

Conformationally gated photoinduced processes within photosensitizer–acceptor dyads based on ruthenium(II) and osmium(II) polypyridyl complexes with an appended pyridinium group

Lainé

Campagna

Loiseau

2008

Coordination Chemistry Reviews

106

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Synthetic control of excited states. Nonchromophoric ligand variations in polypyridyl complexes of osmium(II)

Cited by 183 publications

References 2 publications

Co‐Ligand Involvement in Ground and Excited States of Electron‐Rich (Polypyridyl)Pt^II Complexes

Co‐Ligand Involvement in Ground and Excited States of Electron‐Rich (Polypyridyl)Pt^II Complexes

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

Conformationally gated photoinduced processes within photosensitizer–acceptor dyads based on ruthenium(II) and osmium(II) polypyridyl complexes with an appended pyridinium group

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Synthetic control of excited states. Nonchromophoric ligand variations in polypyridyl complexes of osmium(II)

Cited by 183 publications

References 2 publications

Co‐Ligand Involvement in Ground and Excited States of Electron‐Rich (Polypyridyl)PtII Complexes

Co‐Ligand Involvement in Ground and Excited States of Electron‐Rich (Polypyridyl)PtII Complexes

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

Conformationally gated photoinduced processes within photosensitizer–acceptor dyads based on ruthenium(II) and osmium(II) polypyridyl complexes with an appended pyridinium group

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Co‐Ligand Involvement in Ground and Excited States of Electron‐Rich (Polypyridyl)Pt^II Complexes

Co‐Ligand Involvement in Ground and Excited States of Electron‐Rich (Polypyridyl)Pt^II Complexes