Impact of local compressive stress on the optical transitions of single organic dye molecules

Abstract

The ability to mechanically control the optical properties of individual molecules is a grand challenge in nanoscience and could enable the manipulation of chemical reactivity at the single-molecule level. In the past, light has been used to alter the emission wavelength of individual molecules1 or modulate the energy transfer quantum yield between them2. Furthermore, tensile stress has been applied to study the force dependence of protein folding/unfolding3,4,5 and of the chemistry and photochemistry of single molecules6,7,8,9, although in these mechanical experiments the strength of the weakest bond limits the amount of applicable force. Here, we show that compressive stress modifies the photophysical properties of individual dye molecules. We use an atomic force microscope tip to prod individual molecules adsorbed on a surface and follow the effect of the applied force on the electronic states of the molecule by fluorescence spectroscopy. Applying a localized compressive force on an isolated molecule induces a stress that is redistributed throughout the structure. Accordingly, we observe reversible spectral shifts and even shifts that persist after retracting the microscope tip, which we attribute to transitions to metastable states. Using quantum-mechanical calculations, we show that these photophysical changes can be associated with transitions among the different possible conformers of the adsorbed molecule.

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Figure 1: Simultaneous AFM and CFM experiment.
Figure 2: Structure and optical spectra of TDI–4PDI.
Figure 3: Force–distance experiments on single TDI–4PDI molecules.
Figure 4: Force-induced transitions into metastable states.
Figure 5: Force–spectral shift correlation function Ct).

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Acknowledgements

S.S. acknowledges support from the Deutsche Forschungsgemeinschaft (IRTG 1404).

Author information

S.S. performed the experiments and analysed the data. G.H. and T.B. designed and supervised the research. Synthesis and chemical analysis of TDI–4PDI were performed by I.O. and K.M. DFT calculations were performed by G.D. The experimental set-up was built by G.H. The manuscript was written by G.H., S.S. and T.B.

Correspondence to Gerald Hinze or Thomas Basché.

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Stöttinger, S., Hinze, G., Diezemann, G. et al. Impact of local compressive stress on the optical transitions of single organic dye molecules. Nature Nanotech 9, 182–186 (2014). https://doi.org/10.1038/nnano.2013.303

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