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A multi-stage single photochrome system for controlled photoswitching responses

Abstract

The ability of molecular photoswitches to convert on/off responses into large macroscale property change is fundamental to light-responsive materials. However, moving beyond simple binary responses necessitates the introduction of new elements that control the chemistry of the photoswitching process at the molecular scale. To achieve this goal, we designed, synthesized and developed a single photochrome, based on a modified donor–acceptor Stenhouse adduct (DASA), capable of independently addressing multiple molecular states. The multi-stage photoswitch enables complex switching phenomena. To demonstrate this, we show spatial control of the transformation of a three-stage photoswitch by tuning the population of intermediates along the multi-step reaction pathway of the DASAs without interfering with either the first or final stage. This allows for a photonic three-stage logic gate where the secondary wavelength solely negates the input of the primary wavelength. These results provide a new strategy to move beyond traditional on/off binary photochromic systems and enable the design of future molecular logic systems.

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Fig. 1: Multi-stage photoswitches to move beyond binary systems.
Fig. 2: A DASA as a single photochrome multi-stage photoswitch.
Fig. 3: Stabilizing Stage II through structural modification in DASA architecture.
Fig. 4: Dual wavelength control of DASA 2 switching mechanism by intercepting Stage II.
Fig. 5: Intercepting a transient intermediate allows for advanced control of photoswitch population.

Data availability

All data (experimental procedures and characterization data) supporting the findings of this study are available within the Article and its Supplementary Information. Source data are provided with this paper.

Code availability

The codes used for the analysis of the raw experimental and simulation data and for the generation of the manuscript figures are available from the corresponding authors upon request.

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Acknowledgements

This research reported here was supported by the Office of Naval Research through the MURI of Photomechanical Materials Systems (ONR N00014-18-1-2624). F.S. thanks the German National Academic foundation for an ERP-Fellowship. N.D.D. was supported by the Institute for Collaborative Biotechnologies under Contract Number W911NF-09-D-00010. D.M.S. is grateful to the National Science Foundation for a graduate fellowship. Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the US Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344. The authors acknowledge the use of the NSF (grant no. MRI-1920299) for the acquisition of Bruker 500 MHz and 400 MHz NMR instruments. We also want to thank K. Culhane for the table-of-contents graphic.

Author information

Authors and Affiliations

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Contributions

The project was conceptualized by F.S., N.D.D. and J.R.d.A. while the experimental design and methodology were developed by F.S., D.M.S., U.R. and N.D.D. The experiments were conducted by F.S., N.D.D. and M.S.Z. while D.M.S., U.R., J.M. and T.J.M. performed the ab initio simulations. The data were analysed by F.S., D.M.S., U.R., N.D.D., J.M., T.J.M. and J.R.d.A. The project was supervised by T.J.M. and J.R.d.A. The manuscript was written by F.S., D.M.S., U.R. and J.R.d.A. and edits were conducted by all authors.

Corresponding authors

Correspondence to Todd. J. Martínez or Javier Read de Alaniz.

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Nature Chemistry thanks Michael Lerch, Helena Shepherd and Brian Wagner for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–53, Tables 1–6, Schemes 1 and 2 and Discussion.

Supplementary Video 1

DASA 2 in a glass tube at 250 μM in toluene. Irradiation with a 530 nm LED at 1 mW total output. The transformation from A to B/B′ and subsequent bleaching to C isomers can be observed. The video is sped up to 80× real time.

Supplementary Video 2

DASA 2 in two glass tubes at 125 μM in toluene. Both samples are continuously irradiated with a 530 nm LED (1 mW). The right sample is intermittently (from 5 to 10 min and from 15 to 20 min) irradiated coaxially with a 660 nm LED (30 mW). This video shows how the transformation from A to C can be interrupted with a secondary wavelength effectively locking in the bleaching front at set distances. The video is sped up to 160× real time.

Supplementary Video 3

DASA 2 in a glass tube at 250 μM in toluene. The sample is continuously irradiated with strong white light. A 660 nm LED (73 mW) is used to protect an area from bleaching. The area which is irradiated with a 660 nm LED shows DASA 2 in the open form A after irradiation with white light. The video is sped up to 160× real time.

Supplementary Video 4

DASA 2 in a glass tube at 250 μM in toluene. The sample is continuously irradiated with a 530 nm LED (1 mW). A 660 nm LED (73 mW) is set up to provide perpendicular irradiation. This video shows how the transformation from A to C can be gated at a distance by interfering with the photoswitching process. The video is sped up to 160× real time.

Supplementary Video 5

DASA 2 in two glass tubes at 250 μM in toluene. Both samples are continuously irradiated with a 530 nm LED (1 mW). A 660 nm LED (73 mW) is set up to provide perpendicular irradiation with one tube (T1) in front of the other (T2). The 660 nm LED is turned on as soon as the bleaching front of tube T1 has passed by. This video shows how the transformation from A to C can be interrupted through the photoproduct C without interfering with the photoswitching process in tube T1. The video is sped up to 160× real time.

Supplementary Video 6

DASA 2 in two glass tubes at 125 μM in toluene. The right sample is continuously irradiated with a 530 nm LED (1 mW). The right sample is irradiated with a 660 nm LED (30 mW) from 5 to 10 min and from 15 to 20 min. The left sample is irradiated with a 530 nm LED that is interrupted during these times. This shows no significant difference between turning a 660 nm LED on while irradiating with a 530 nm LED or turning the 530 nm LED off. The video is sped up to 160× real time.

Supplementary Video 7

Full mechanism of DASA 2 from A to C′′′′.

Supplementary Data 1

DFT S0 geometries.

Source data

Source Data Fig. 2

Source data for UV–vis data.

Source Data Fig. 3

Source data for time-dependent UV–vis data.

Source Data Fig. 4

Source data for UV–vis and time-dependent UV–vis data; light intensity measurements.

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Stricker, F., Sanchez, D.M., Raucci, U. et al. A multi-stage single photochrome system for controlled photoswitching responses. Nat. Chem. 14, 942–948 (2022). https://doi.org/10.1038/s41557-022-00947-8

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