Luminescence properties of organometallic complexes

Lees, Alistair J.

doi:10.1021/cr00080a003

Cited by 502 publications

(318 citation statements)

References 100 publications

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“…The lifetime in the presence of dioxygen is considerably shorter ( = 3.97  0.57 s) compared to degassed solutions ( = 10.65  0.14 s), which is a common phenomenon and characteristic for 3 MLCT emissions. 18,38 Also in accordance with our tentative assignment of a charge-transfer transition is the observation of a strong solvent-dependence of the quantum yields for this band (Table 1). Table S1 in the ESI).…”

supporting

confidence: 88%

Synthesis, characterisation and bioimaging of a fluorescent rhenium-containing PNA bioconjugate

et al. 2012

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A new rhenium tricarbonyl complex of a bis(quinoline)-derived ligand (2-azido-N,N-bis((quinolin-2-yl)methyl)ethanamine, L-N(3)), namely [Re(CO)(3)(L-N(3))]Br was synthesized and characterized indepth, including by X-ray crystallography. [Re(CO)(3)(L-N(3))]Br exhibits a strong UV absorbance in the range 300-400 nm with a maximum at 322 nm, and upon photoexcitation, shows two distinct emission bands at about 430 and 560 nm in various solvents (water, ethylene glycol). [Re(CO)(3)(L-N(3))]Br could be conjugated, on a solid phase, to a peptide nucleic acid (PNA) oligomer using the copper(I)-catalyzed azide-alkyne cycloaddition reaction (Cu-AAC, "click" chemistry) and an alkyne-containing PNA building block to give Re-PNA. It was demonstrated that upon hybridisation with a complementary DNA strand (DNA), the position of the maxima and emission intensity for the hybrid Re-PNA·DNA remained mainly unchanged compared to those of the single strand Re-PNA. The rhenium-containing PNA oligomer Re-PNA could be then mediated in living cells where they have been shown to be non-toxic contrary to the general notion that organometallic compounds are usually unstable under physiological conditions and/or cytotoxic. Furthermore, Re-PNA could be detected in living cells using fluorescent microscopy.

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supporting

confidence: 88%

Synthesis, characterisation and bioimaging of a fluorescent rhenium-containing PNA bioconjugate

et al. 2012

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“…2a and Table 1. Based on their intensities, these transitions are spin-allowed bands from the singlet electronic ground state, which have typical molar absorptivities of lo3-lo4 M-' cm-' (16). Weak, low-energy bands were observed for these complexes at ca.…”

Section: Resultsmentioning

confidence: 97%

Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Bayrakdarian¹,

Davis²,

Reber³

et al. 1996

Can. J. Chem.

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Abstract:The electronic structures of two types of transition metal indenyl complexes have been studied. The first type, a series of (Ind)Ni(PPh,)X compounds (Ind = indenyl, 1-Me-indenyl; X = C1, Br, Me) was investigated by absorption spectroscopy and Extended Huckel Molecular Orbital calculations. The energy differences between calculated levels are in good agreement with experimental band positions. For example, the lowest energy singlet-singlet band maximum for (Ind)Ni(PPh,)Cl is at 19 500 cm-I and the calculated HOMO-LUMO difference is 19 817 cm-I. For X = Me, the calculated energy difference increases to 21 930 cm-I and the corresponding absorption band is at 22 500 cm-I. The influence of the metal-ligand interactions on the molecular orbitals is discussed. The second category of indenyk'the bis(indeny1) compounds of Ni and Ru, show absorption spectra that are markedly different from those of nickelocene and ruthenocene. For example, in comparison to nickelocene, the first absorption band of Ni(Ind), is 5700 cm-' higher in energy and is more intense by two orders of magnitude; in contrast, the first absorption maximum of Ru(Ind)? is 6600 cm-' lower in energy than observed for ruthenocene. The characteristics and relaxation dynamics of the lowest energy excited states are discussed.Key words: absorption spectroscopy, indenyl, nickel, ruthenium, EHMO analysis.

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“…This observation is consistent with previous studies which confirmed that optical population of the triplet state in Group 6 metal complexes is only possible for tungsten and not for chromium or molybdenum complexes. 32,33 Two excitation wavelengths were used in these Table 1 The observed and calculated ν CO bands for (1), (3), (4), (5) The UV/Vis spectra of (1) (a) and (4) (b) recorded in n-heptane solution. The singlet to triplet transition is evident as a shoulder in the spectrum of (4), this feature is absent in the spectrum of (1).…”

Section: Picosecond Time Resolved Infrared Studiesmentioning

confidence: 99%

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

et al. 2015

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propanone singlet excited state was detected on the reaction path to the metallaketene species. This metallacyclopropanone excited state species has a lifetime of less than 100 ps and a characteristic bridging carbonyl band at 1770 cm −1 . The tungsten ketene species was also detected but in contrast to the chromium system, this forms directly from a low-lying triplet excited state. The electrochemical release of CO showed a greater efficiency for the chromium complex when compared to the tungsten.

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Luminescence properties of organometallic complexes

Cited by 502 publications

References 100 publications

Synthesis, characterisation and bioimaging of a fluorescent rhenium-containing PNA bioconjugate

Synthesis, characterisation and bioimaging of a fluorescent rhenium-containing PNA bioconjugate

Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

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Luminescence properties of organometallic complexes

Cited by 502 publications

References 100 publications

Synthesis, characterisation and bioimaging of a fluorescent rhenium-containing PNA bioconjugate

Synthesis, characterisation and bioimaging of a fluorescent rhenium-containing PNA bioconjugate

Absorption spectroscopy of (Ind)Ni(PPh3)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)2 (M = Ni, Ru; Ind = indenyl)

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)5MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

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Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory