Internal Stark effect of single-molecule fluorescence

Vasilev, Kirill; Doppagne, Benjamin; Neuman, Tomáš; Rosławska, Anna; Bulou, Hervé; Boeglin, Alex; Scheurer, F.; Schull, Guillaume

doi:10.1038/s41467-022-28241-8

Cited by 10 publications

(8 citation statements)

References 57 publications

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“…A similar situation was previously found for other nonluminescent Pc molecules. 40,41 The S 1 state may still be accessible by applying larger voltages that allow tunneling out of lower-lying occupied (or into higher-lying unoccupied) orbitals. This excites the molecule into a higher doublet state (D x ) and permits access to S 1 upon discharging.…”

Section: ■ Discussionmentioning

confidence: 99%

Activating the Fluorescence of a Ni(II) Complex by Energy Transfer

Hung,

Godinez-Loyola,

Steinbrecher

et al. 2024

J. Am. Chem. Soc.

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Luminescence of open-shell 3d metal complexes is often quenched due to ultrafast intersystem crossing (ISC) and cooling into a dark metal-centered excited state. We demonstrate successful activation of fluorescence from individual nickel phthalocyanine (NiPc) molecules in the junction of a scanning tunneling microscope (STM) by resonant energy transfer from other metal phthalocyanines at low temperature. By combining STM, scanning tunneling spectroscopy, STM-induced luminescence, and photoluminescence experiments as well as time-dependent density functional theory, we provide evidence that there is an activation barrier for the ISC, which, in most experimental conditions, is overcome. We show that this is also the case in an electroluminescent tunnel junction where individual NiPc molecules adsorbed on an ultrathin NaCl decoupling film on a Ag(111) substrate are probed. However, when an MPc (M = Zn, Pd, Pt) molecule is placed close to NiPc by means of STM atomic manipulation, resonant energy transfer can excite NiPc without overcoming the ISC activation barrier, leading to Q-band fluorescence. This work demonstrates that the thermally activated population of dark metal-centered states can be avoided by a designed local environment at low temperatures paired with directed molecular excitation into vibrationally cold electronic states. Thus, we can envisage the use of luminophores based on more abundant transition metal complexes that do not rely on Pt or Ir by restricting vibration-induced ISC.

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Section: ■ Discussionmentioning

confidence: 99%

Activating the Fluorescence of a Ni(II) Complex by Energy Transfer

Hung,

Godinez-Loyola,

Steinbrecher

et al. 2024

J. Am. Chem. Soc.

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“…Moreover, the emitted light from the molecular excitonic mode can also be squeezed, along with the plasmon mode. Our results are of immediate relevance to STM single molecular junctions aiming to detect and control plasmon-enhanced light–matter interactions − and take an important step toward the realization of quantum information processing using single molecules.…”

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confidence: 82%

Plasmon Squeezing in Single-Molecule Junctions

2022

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Scanning tunneling microscope (STM)-induced luminescence provides an ideal platform for electrical generation and the atomic-scale manipulation of nonclassical states of light. However, despite its extreme importance in quantum technologies, squeezed light emission with reduced quantum fluctuations has hitherto not been demonstrated in such a platform. Here, we theoretically predict that the emitted light from the plasmon mode can be squeezed in an STM single molecular junction subject to an external laser drive. Going beyond the traditional paradigm that generates squeezing with the quadratic interaction of photons, our prediction explores the molecular coherence involved in an anharmonic energy spectrum of a coupled plasmon−molecule−exciton system. Furthermore, we show that, by selectively exciting the energy ladder, the squeezed plasmon can show either sub-or super-Poissonian statistical properties. We also demonstrate that, following the same principle, the molecular excitonic mode can be squeezed simultaneously.

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“…The other effect influencing fluorescence spectra of ICT dyes is electrofluorochromism that is known as internal Stark effect observed in fluorescence [42,43]. This phenomenon is caused by direct interaction of the ground-and excited-state dipoles with the applied electric field that can occur on molecular scale due to the presence of nearby charges.…”

Section: Excited-state Intramolecular Charge Transfer (Ict)mentioning

confidence: 99%

Dual emission and its λ-ratiometric detection in analytical fluorimetry. Pt. I. Basic mechanisms of generating the reporter signal

Demchenko

2023

Methods Appl. Fluoresc.

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The wavelength-ratiometric techniques gain increasing popularity in fluorescence probing and sensing for providing inner reference to output signal and removing instrumental artefacts, in this way increasing the sensitivity and reliability of assays. Recent developments demonstrate that such approach can allow achieving much more, with the application of broad range of novel molecular and nanoscale fluorophores (luminophores), exploring the whole power of photophysical and photochemical effects and using extended range of assay formats. Simplicity of detection and potentially rich content of output data allows realizing these techniques in different simplified, miniaturized and multiplexing devices. The latter issues are discussed in Pt. II of these series.

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Internal Stark effect of single-molecule fluorescence

Cited by 10 publications

References 57 publications

Activating the Fluorescence of a Ni(II) Complex by Energy Transfer

Activating the Fluorescence of a Ni(II) Complex by Energy Transfer

Plasmon Squeezing in Single-Molecule Junctions

Dual emission and its λ-ratiometric detection in analytical fluorimetry. Pt. I. Basic mechanisms of generating the reporter signal

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