Iminothioindoxyl as a molecular photoswitch with 100 nm band separation in the visible range

Year: 2019

Authors: Hoorens M.W.H., Medved M., Laurent A.D., Di Donato M., Fanetti S., Slappendel L., Hilbers M., Feringa B., Buma WJ., Szymanski W.

Autors Affiliation: Univ Groningen, Univ Med Ctr Groningen, Med Imaging Ctr, Dept Radiol, Hanzepl 1, NL-9713 GZ Groningen, Netherlands; Univ Groningen, Stratingh Inst Chem, Ctr Syst Chem, Fac Sci & Engn, Nijenborgh 7, NL-9747 AG Groningen, Netherlands; Palacky Univ Olomouc, Reg Ctr Adv Technol & Mat, Fac Sci, Slechtitelu 27, CZ-77146 Olomouc, Czech Republic; Matej Bel Univ, Dept Chem, Fac Nat Sci, Tajovskeho 40, SK-97400 Banska Bystrica, Slovakia; Univ Nantes, CNRS, CEISAM, UMR 6230, BP 92208,2 Rue Houssiniere, F-44322 Nantes 3, France; European Lab Non Linear Spect LENS, Via N Carrara 1, I-50019 Sesto Fiorentino, Italy; INO, Largo Fermi 6, I-50125 Florence, Italy; Univ Amsterdam, Vant Hoff Inst Mol Sci, Sci Pk 904, NL-1098 XH Amsterdam, Netherlands; Radboud Univ Nijmegen, FELIX Lab, Inst Mol & Mat, Toernooiveld 7c, NL-6525 ED Nijmegen, Netherlands; Univ Florence, Dept Chem Ugo Shiff, Via Lastruccia 3-13, I-50019 Sesto Fiorentino, FI, Italy

Abstract: Light is an exceptional external stimulus for establishing precise control over the properties and functions of chemical and biological systems, which is enabled through the use of molecular photoswitches. Ideal photoswitches are operated with visible light only, show large separation of absorption bands and are functional in various solvents including water, posing an unmet challenge. Here we show a class of fully-visible-light-operated molecular photoswitches, lminothioindoxyls (ITIs) that meet these requirements. ITIs show a band separation of over 100 nm, isomerize on picosecond time scale and thermally relax on millisecond time scale. Using a combination of advanced spectroscopic and computational techniques, we provide the rationale for the switching behavior of ITIs and the influence of structural modifications and environment, including aqueous solution, on their photochemical properties. This research paves the way for the development of improved photo-controlled systems for a wide variety of applications that require fast responsive functions.

Journal/Review: NATURE COMMUNICATIONS

Volume: 10      Pages from: 2390-1  to: 2390-11

More Information: The support of the Netherlands Organization for Scientific Research (NWO-CW VIDI grant 723.014.001 to W.S.) and the European Union Horizon 2020 Research and Innovation Programme (grant agreement: “Laserlab-Europe”, H2020EC-GA 654148) is kindly acknowledged. M.M. acknowledges the ERDF/ESF project “Nanotechnologies for Future” (CZ.02.1.01/0.0/0.0/16_019/0000754), the Slovak Research and Development Agency (project no. APVV-15-0105) and CMST COST Action CM1405 MOLIM: MOLecules In Motion. This research used resources of (1) the GENCI-CINES/IDRIS (Grants A0020805 l 17), (2) CCIPL (Centre de Calcul Intensif des Pays de Loire), (3) the HPCC of the Matej Bel University in Banska Bystrica (ITMS 26230120002 and 26210120002 supported by the Research and Development Operational Programme funded by the ERDF). This work was supported financially by the European Research Council (ERC; advanced grant no. 694345 to B.L.F.) and the Ministry of Education, Culture and Science (Gravitation program no. 024.001.035). We thank Pieter van der Meulen for assistance with the in NMR irradiation experiments. M.M. and A.D.L. thank Denis Jacquemin for careful advice and fruitful discussions. We thank Mark Koenis for recording room-temperature IR spectra.
KeyWords: AZOBENZENE PHOTOSWITCHES; INFRARED-SPECTROSCOPY; EXCITED-STATES; LIGHT; PHOTOCONTROL; DERIVATIVES; PEPTIDES; PROTEIN; DESIGN
DOI: 10.1038/s41467-019-10251-8

Citations: 49
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