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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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.
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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.
References
Feringa, B. L. & Browne, W. R. (eds) Molecular Switches 2nd edn, Vol. 1 (Wiley-VCH Verlag GmbH & Co. KGaA, 2011).
Iamsaard, S. et al. Conversion of light into macroscopic helical motion. Nat. Chem. 6, 229–235 (2014).
Li, J., Zhou, X. & Liu, Z. Recent advances in photoactuators and their applications in intelligent bionic movements. Adv. Opt. Mater. 8, 2000886 (2020).
Soberats, B. et al. Macroscopic photocontrol of ion-transporting pathways of a nanostructured imidazolium-based photoresponsive liquid crystal. J. Am. Chem. Soc. 136, 9552–9555 (2014).
Nie, H. et al. Light-controllable ionic conductivity in a polymeric ionic liquid. Angew. Chem. Int. Ed. 59, 5123–5128 (2020).
Qiu, Q., Shi, Y. & Han, G. G. D. Solar energy conversion and storage by photoswitchable organic materials in solution, liquid, solid, and changing phases. J. Mater. Chem. C 9, 11444–11463 (2021).
Goulet-Hanssens, A., Eisenreich, F. & Hecht, S. Enlightening materials with photoswitches. Adv. Mater. 32, 1905966 (2020).
Browne, W. R. & Feringa, B. L. Making molecular machines work. Nat. Nanotechnol. 1, 25–35 (2006).
Bandara, H. M. D. & Burdette, S. C. Photoisomerization in different classes of azobenzene. Chem. Soc. Rev. 41, 1809–1825 (2012).
Su, X. & Aprahamian, I. Hydrazone-based switches, metallo-assemblies and sensors. Chem. Soc. Rev. 43, 1963–1981 (2014).
Irie, M. Diarylethenes for memories and switches. Chem. Rev. 100, 1685–1716 (2000).
Irie, M., Fukaminato, T., Matsuda, K. & Kobatake, S. Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem. Rev. 114, 12174–12277 (2014).
Minkin, V. I. Photo-, thermo-, solvato-, and electrochromic spiroheterocyclic compounds. Chem. Rev. 104, 2751–2776 (2004).
Daub, J., Knöchel, T. & Mannschreck, A. Photosensitive dihydroazulenes with chromogenic properties. Angew. Chem. Int. Ed. 23, 960–961 (1984).
Bouas-Laurent, H. & Dürr, H. Organic photochromism. Pure Appl. Chem. 73, 639–665 (2001).
Mrozek, T., Görner, H. & Daub, J. Towards multifold cycloswitching of biphotochromes: investigation on a bond-fused dihydroazulene/vinylheptafulvene and dithienylethene/dihydrothienobenzothiophene. Chem. Commun.1487–1488 (1999).
Fihey, A., Perrier, A., Browne, W. R. & Jacquemin, D. Multiphotochromic molecular systems. Chem. Soc. Rev. 44, 3719–3759 (2015).
Nie, H., Self, J. L., Kuenstler, A. S., Hayward, R. C. & Read de Alaniz, J. Multiaddressable photochromic architectures: from molecules to materials. Adv. Opt. Mater. 7, 1900224 (2019).
Perrier, A., Maurel, F. & Jacquemin, D. Single molecule multiphotochromism with diarylethenes. Acc. Chem. Res. 45, 1173–1182 (2012).
Andréasson, J. & Pischel, U. Light-stimulated molecular and supramolecular systems for information processing and beyond. Coord. Chem. Rev. 429, 213695 (2021).
Zulfikri, H. et al. Taming the complexity of donor–acceptor Stenhouse adducts: infrared motion pictures of the complete switching pathway. J. Am. Chem. Soc. 141, 7376–7384 (2019).
Mallo, N. et al. Hydrogen-bonding donor-acceptor Stenhouse adducts. ChemPhotoChem 4, 407–412 (2020).
Lerch, M. M., Szymański, W. & Feringa, B. L. The (photo)chemistry of Stenhouse photoswitches: guiding principles and system design. Chem. Soc. Rev. 47, 1910–1937 (2018).
Helmy, S. et al. Photoswitching using visible light: a new class of organic photochromic molecules. J. Am. Chem. Soc. 136, 8169–8172 (2014).
Mallo, N. et al. Photochromic switching behaviour of donor–acceptor Stenhouse adducts in organic solvents. Chem. Commun. 52, 13576–13579 (2016).
Lerch, M. M., Wezenberg, S. J., Szymanski, W. & Feringa, B. L. Unraveling the photoswitching mechanism in donor–acceptor Stenhouse adducts. J. Am. Chem. Soc. 138, 6344–6347 (2016).
Lerch, M. M. et al. Tailoring photoisomerization pathways in donor–acceptor Stenhouse adducts: the role of the hydroxy group. J. Phys. Chem. A 122, 955–964 (2018).
Hemmer, J. R. J. R. et al. Controlling dark equilibria and enhancing donor–acceptor Stenhouse adduct photoswitching properties through carbon acid design. J. Am. Chem. Soc. 140, 10425–10429 (2018).
Hemmer, J. R. et al. Tunable visible and near infrared photoswitches. J. Am. Chem. Soc. 138, 13960–13966 (2016).
Lerch, M. M., Hansen, M. J., Velema, W. A., Szymanski, W. & Feringa, B. L. Orthogonal photoswitching in a multifunctional molecular system. Nat. Commun. 7, 12054 (2016).
Di Donato, M. et al. Shedding light on the photoisomerization pathway of donor–acceptor Stenhouse Adducts. J. Am. Chem. Soc. 139, 15596–15599 (2017).
Lerch, M. M. et al. Solvent effects on the actinic step of donor–acceptor Stenhouse adduct photoswitching. Angew. Chem. Int. Ed. 57, 8063–8068 (2018).
Laurent, A. D., Medved, M. & Jacquemin, D. Using time-dependent density functional theory to probe the nature of donor–acceptor Stenhouse adduct photochromes. ChemPhysChem 17, 1846–1851 (2016).
Sanchez, D. M., Raucci, U., Ferreras, K. N. & Martínez, T. J. Putting photomechanical switches to work: an ab initio multiple spawning study of donor–acceptor Stenhouse adducts. J. Phys. Chem. Lett. 11, 7901–7907 (2020).
Mallo, N. et al. Structure-function relationships of donor-acceptor Stenhouse adduct photochromic switches. Chem. Sci. 9, 8242–8252 (2018).
Clerc, M. et al. Promoting the furan ring opening reaction to access new donor–acceptor Stenhouse adducts with hexafluoroisopropanol. Angew. Chem. Int. Ed. 60, 10219–10227 (2021).
García-Iriepa, C., Marazzi, M. & Sampedro, D. From light absorption to cyclization: structure and solvent effects in donor-acceptor Stenhouse adducts. ChemPhotoChem 3, 866–873 (2019).
García-Iriepa, C. & Marazzi, M. Level of theory and solvent effects on DASA absorption properties prediction: comparing TD-DFT, CASPT2 and NEVPT2. Materials 10, 1025 (2017).
Berraud-Pache, R. et al. Redesigning donor–acceptor Stenhouse adduct photoswitches through a joint experimental and computational study. Chem. Sci. 12, 2916–2924 (2021).
Sroda, M. M., Stricker, F., Peterson, J. A., Bernal, A. & Read de Alaniz, J. Donor–acceptor Stenhouse adducts: exploring the effects of ionic character. Chem. Eur. J. 27, 4183–4190 (2020).
Sanchez, D. M., Raucci, U. & Martínez, T. J. In silico discovery of multistep chemistry initiated by a conical intersection: the challenging case of donor–acceptor Stenhouse adducts. J. Am. Chem. Soc. 143, 20015–20021 (2021).
Stranius, K. & Börjesson, K. Determining the photoisomerization quantum yield of photoswitchable molecules in solution and in the solid state. Sci Rep. 7, 41145 (2017).
Terrones, G. & Pearlstein, A. J. Effects of optical attenuation and consumption of a photobleaching initiator on local initiation rates in photopolymerizations. Macromolecules 34, 3195–3204 (2001).
Dolinski, N. D. et al. A versatile approach for in situ monitoring of photoswitches and photopolymerizations. ChemPhotoChem 1, 125–131 (2017).
Dolinski, N. D. et al. Solution mask liquid lithography (SMaLL) for one-step, multimaterial 3D printing. Adv. Mater. 30, 1800364 (2018).
Hohenstein, E. G., Luehr, N., Ufimtsev, I. S. & Martínez, T. J. An atomic orbital-based formulation of the complete active space self-consistent field method on graphical processing units. J. Chem. Phys. 142, 224103 (2015).
Snyder, J. W., Curchod, B. F. E. & Martínez, T. J. GPU-accelerated state-averaged complete active space self-consistent field interfaced with ab initio multiple spawning unravels the photodynamics of provitamin D3. J. Phys. Chem. Lett. 7, 2444–2449 (2016).
Snyder, J. W., Fales, B. S., Hohenstein, E. G., Levine, B. G. & Martínez, T. J. A direct-compatible formulation of the coupled perturbed complete active space self-consistent field equations on graphical processing units. J. Chem. Phys. 146, 174113 (2017).
Ufimtsev, I. S. & Martinez, T. J. Strategies for two-electron integral evaluation. J. Chem. Theory Comput. 4, 222–231 (2008).
Ufimtsev, I. S. & Martinez, T. J. Quantum chemistry on graphical processing units. 2. Direct self-consistent-field implementation. J. Chem. Theory Comput. 5, 1004–1015 (2009).
Ufimtsev, I. S. & Martinez, T. J. Quantum chemistry on graphical processing units. 3. Analytical energy gradients, geometry optimization, and first principles molecular dynamics. J. Chem. Theory Comput. 5, 2619–2628 (2009).
Kästner, J. et al. DL-FIND: an open-source geometry optimizer for atomistic simulations. J. Phys. Chem. A 113, 11856–11865 (2009).
Henkelman, G. & Jónsson, H. A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. J. Chem. Phys. 111, 7010–7022 (1999).
ChemShell: A Computational Chemistry Shell; www.chemshell.org
Sherwood, P. et al. QUASI: A general purpose implementation of the QM/MM approach and its application to problems in catalysis. J. Mol. Struc. (Theochem.) 632, 1–28 (2003).
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.
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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.
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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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DOI: https://doi.org/10.1038/s41557-022-00947-8
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