Cyclometallated platinum(ii) complexes incorporating ethynyl–flavone ligands: switching between triplet and singlet emission induced by selective binding of Pb2+ ions

Lanoë, Pierre‐Henri; Fillaut, Jean‐Luc; Toupet, Loı̈c; Williams, J. A. Gareth; Bozec, Hubert Le; Guerchais, Véronique

doi:10.1039/b806935b

Cited by 76 publications

(45 citation statements)

References 22 publications

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“…Phosphorescent metal complexes are generally good signaling systems because phosphorescent signals show many advantages such as sensitive emission properties in response to the local environment, strong single-photon excitation in the visible region, relatively long emission lifetimes and large Stokes shifts for 5) that can switch from triplet to singlet emission in response to Pb 2+ binding. 50 The t Bu groups sterically inhibit the undesirable intermolecular interactions that usually cause concentration-dependent self-quenching of the emission. Complex 19b shows 3 IL phosphorescence associated with the anchored flavone perturbed by the Pt centre (t B 20 ms), but switches largely to flavone-localized 1 IL fluorescence (t B 2 ns) after selective binding of Pb 2+ .…”

Section: Sensors For Metal Ionsmentioning

confidence: 99%

Cyclometallated tridentate platinum(ii) arylacetylide complexes: old wine in new bottles

et al. 2019

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Section: Sensors For Metal Ionsmentioning

confidence: 99%

Cyclometallated tridentate platinum(ii) arylacetylide complexes: old wine in new bottles

et al. 2019

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“…[14, [16][17][18][19][20] However, the photophysics of these dyads are very often elusive; for example, the phosphorescence was quenched and short T 1 lifetimes were observed when perylenediimide (PDI) and boron-dipyrromethene (BODIPY) were used for the preparation of Pt II and Ir III complexes. [21,22] On the other hand, BODIPY is a particularly interesting chromophore, [23,24] and has been incorporated into Pt II , Ru II , and Ir III complexes to afford visible-light harvesting and long-lived T 1 excited states.…”

Section: Introductionmentioning

confidence: 99%

Long‐Lived Room‐Temperature Near‐IR Phosphorescence of BODIPY in a Visible‐Light‐Harvesting N^C^N Pt^II–Acetylide Complex with a Directly Metalated BODIPY Chromophore

Zhao

Guo

et al. 2012

Chemistry A European J

141

126

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Room-temperature long-lived near-IR phosphorescence of boron-dipyrromethene (BODIPY) was observed (λ(em) = 770 nm, Φ(P) = 3.5 %, τ(P) = 128.4 μs). Our molecular-design strategy is to attach Pt(II) coordination centers directly onto the BODIPY π-core using acetylide bonds, rather than on the periphery of the BODIPY core, thus maximizing the heavy-atom effect of Pt(II). In this case, the intersystem crossing (ISC) is facilitated and the radiative decay of the T(1) excited state of BODIPY is observed, that is, the phosphorescence of BODIPY. The complex shows strong absorption in the visible range (ε = 53,800 M(-1) cm(-1) at 574 nm), which is rare for Pt(II)-acetylide complexes. The complex is dual emissive with (3)MLCT emission at 660 nm and the (3)IL emission at 770 nm. The T(1) excited state of the complex is mainly localized on the BODIPY moiety (i.e. (3)IL state, as determined by steady-state and time-resolved spectroscopy, 77 K emission spectra, and spin-density analysis). The strong visible-light-harvesting ability and long-lived T(1) excite state of the complex were used for triplet-triplet annihilation based upconversion and an upconversion quantum yield of 5.2 % was observed. The overall upconversion capability (η = ε×Φ(UC)) of this complex is remarkable considering its strong absorption. The model complex, without the BODIPY moiety, gives no upconversion under the same experimental conditions. Our work paves the way for access to transition-metal complexes that show strong absorption of visible light and long-lived (3)IL excited states, which are important for applications in photovoltaics, photocatalysis, and upconversions, etc.

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“…The triplet state lifetime of 8 is 48.5 µs and that of 7 is 1.25 µs. Fillaut reported a series of N ^ N ^ C Pt II acetylide complexes with ethynylflavone ligand systems in which the light‐harvesting ability was improved relative to 7 and the triplet excited state lifetimes were prolonged to 12–21 µs …”

Section: Photophysical Properties Of Ptii Complexesmentioning

confidence: 99%

Photophysical Properties of Visible‐Light‐Harvesting Pt^II Bis(acetylide) Complexes

Yang

Zhao

2016

Eur J Inorg Chem

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PtII complexes have attracted much attention due to their readily derivatizable molecular structures and efficient production of triplet excited states and have been extensively used in many areas. Conventional PtII complexes usually exhibit small molar absorption coefficients in the visible spectral region, and the triplet excited state lifetimes are short. However, for applications such as photocatalysis, triplet–triplet annihilation (TTA) upconversion, nonlinear optics, etc., visible‐light‐harvesting PtII bis(acetylide) complexes with long‐lived triplet excited state are cucial. We summarize strategies directed towards achieving these goals, through the attachment of appropriate strong visible‐light‐harvesting organic chromophores to the ligand to switch the S0→1MLCT (metal‐to‐ligand charge transfer) transition to the S0→1IL (intraligand) transition (π–π*) and to switch the lowest triplet excited state from the 3MLCT to the 3IL state. We also summarize the properties of PtII bis(acetylide) complexes that show broadband absorption and reverse saturate absorption for application in nonlinear optics. Singlet and triplet energy transfer and localization of the triplet excited state in multiple‐chromophore complexes are also discussed.

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Cyclometallated platinum(ii) complexes incorporating ethynyl–flavone ligands: switching between triplet and singlet emission induced by selective binding of Pb2+ ions

Cited by 76 publications

References 22 publications

Cyclometallated tridentate platinum(ii) arylacetylide complexes: old wine in new bottles

Cyclometallated tridentate platinum(ii) arylacetylide complexes: old wine in new bottles

Long‐Lived Room‐Temperature Near‐IR Phosphorescence of BODIPY in a Visible‐Light‐Harvesting N^C^N Pt^II–Acetylide Complex with a Directly Metalated BODIPY Chromophore

Photophysical Properties of Visible‐Light‐Harvesting Pt^II Bis(acetylide) Complexes

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Cyclometallated platinum(ii) complexes incorporating ethynyl–flavone ligands: switching between triplet and singlet emission induced by selective binding of Pb2+ ions

Cited by 76 publications

References 22 publications

Cyclometallated tridentate platinum(ii) arylacetylide complexes: old wine in new bottles

Cyclometallated tridentate platinum(ii) arylacetylide complexes: old wine in new bottles

Long‐Lived Room‐Temperature Near‐IR Phosphorescence of BODIPY in a Visible‐Light‐Harvesting N^C^N PtII–Acetylide Complex with a Directly Metalated BODIPY Chromophore

Photophysical Properties of Visible‐Light‐Harvesting PtII Bis(acetylide) Complexes

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Product

Resources

About

Long‐Lived Room‐Temperature Near‐IR Phosphorescence of BODIPY in a Visible‐Light‐Harvesting N^C^N Pt^II–Acetylide Complex with a Directly Metalated BODIPY Chromophore

Photophysical Properties of Visible‐Light‐Harvesting Pt^II Bis(acetylide) Complexes