The photophysical behavior of d6 complexes having nearly isoenergetic MLCT and ligand localized excited states

Baba, Aaron I.; Shaw, John R.; Simon, Jerald A.; Thummel, Randolph P.; Schmehl, Russell H.

doi:10.1016/s0010-8545(98)90009-1

Cited by 167 publications

(130 citation statements)

References 40 publications

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“…Oligopyridyl complexes of kinetically inert d 6 metals, e.g., Ru(II), Os(II), have attracted enormous interest in recent decades due to their attractive photophysical properties [1][2][3][4]. These complexes typically exhibit relatively long-lived triplet metal-to-ligand charge transfer ( 3 MLCT) states.…”

Section: Introductionmentioning

confidence: 99%

Towards Water Soluble Mitochondria-Targeting Theranostic Osmium(II) Triazole-Based Complexes

et al. 2016

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Abstract:The complex [Os(btzpy) 2 ][PF 6 ] 2 (1, btzpy = 2,6-bis(1-phenyl-1,2,3-triazol-4-yl)pyridine) has been prepared and characterised. Complex 1 exhibits phosphorescence (λ em = 595 nm, τ = 937 ns, φ em = 9.3% in degassed acetonitrile) in contrast to its known ruthenium(II) analogue, which is non-emissive at room temperature. The complex undergoes significant oxygen-dependent quenching of emission with a 43-fold reduction in luminescence intensity between degassed and aerated acetonitrile solutions, indicating its potential to act as a singlet oxygen sensitiser. Complex 1 underwent counterion metathesis to yield [Os(btzpy) 2 ]Cl 2 (1 Cl ), which shows near identical optical absorption and emission spectra to those of 1. Direct measurement of the yield of singlet oxygen sensitised by 1 Cl was carried out (φ ( 1 O 2 ) = 57%) for air equilibrated acetonitrile solutions. On the basis of these photophysical properties, preliminary cellular uptake and luminescence microscopy imaging studies were conducted. Complex 1 Cl readily entered the cancer cell lines HeLa and U2OS with mitochondrial staining seen and intense emission allowing for imaging at concentrations as low as 1 µM. Long-term toxicity results indicate low toxicity in HeLa cells with LD50 >100 µM. Osmium(II) complexes based on 1 therefore present an excellent platform for the development of novel theranostic agents for anticancer activity.

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Section: Introductionmentioning

confidence: 99%

Towards Water Soluble Mitochondria-Targeting Theranostic Osmium(II) Triazole-Based Complexes

et al. 2016

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“…Extending conjugation in ligands can lower the intraligand transition energies until the two are similar, or even make the intraligand excited state lowest. In 1998, Schmehl and co-workers reviewed work involving nearly isoenergetic states of the two sorts, concluding that in a few cases the coexistence of the two states was likely, usually or always in thermal equilibrium and, therefore, showing dual emission from different orbitals with a single lifetime [32]. One instance was their own work of a couple of years earlier [33].…”

Section: 3mentioning

confidence: 99%

So-called “dual emission” for 3MLCT luminescence in ruthenium complex ions: What is really happening?

Magde

Glazer

2016

Coordination Chemistry Reviews

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“…For example, by introduction of electron withdrawing substituents (e.g., SO 2 Me) [34], or acetylene groups [35], lifetimes of the 3 MLCT state up to 580 ns were found, due to the lowering of the 3 MLCT energy which reduces the population of the 3 MC state. However, the most successful strategy to extend the lifetime of the excited state is to equilibrate the emissive 3 MLCT state with a nonemissive triplet state [36]. The ruthenium(II) complex bearing a terpyridine-pyrimidyl-anthranyl ligand reached two lifetimes for the decay of the excited states of 9 ns and 1806 ns [37].…”

Section: Chromophoresmentioning

confidence: 99%

Conversion of CO2 via Visible Light Promoted Homogeneous Redox Catalysis

2012

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Abstract:This review gives an overview on the principles of light-promoted homogeneous redox catalysis in terms of applications in CO 2 conversion. Various chromophores and the advantages of different structures and metal centers as well as optimization strategies are discussed. All aspects of the reduction catalyst site are restricted to CO 2 conversion. An important focus of this review is the question of a replacement of the sacrificial donor which is found in most of the current publications. Furthermore, electronic parameters of supramolecular systems are reviewed with reference to the requisite of chromophores, oxidation and reduction sites.

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The photophysical behavior of d6 complexes having nearly isoenergetic MLCT and ligand localized excited states

Cited by 167 publications

References 40 publications

Towards Water Soluble Mitochondria-Targeting Theranostic Osmium(II) Triazole-Based Complexes

Towards Water Soluble Mitochondria-Targeting Theranostic Osmium(II) Triazole-Based Complexes

So-called “dual emission” for 3MLCT luminescence in ruthenium complex ions: What is really happening?

Conversion of CO2 via Visible Light Promoted Homogeneous Redox Catalysis

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