Taming the Complexity of Donor-Acceptor Stenhouse Adducts: Infrared Motion Pictures of the Complete Switching Pathway

Year: 2019

Authors: Zulfikri H., Koenis MAJ., Lerch MM., Di Donato M., Szymanski W., Filippi C., Feringa BL., Buma WJ.

Autors Affiliation: Univ Twente, MESA Inst Nanotechnol, POB 217, NL-7500 AE Enschede, Netherlands;‎ Univ Amsterdam, Vant Hoff Inst Mol Sci, Sci Pk 904, NL-1098 XH Amsterdam, Netherlands; Univ Groningen, Stratingh Inst Chem, Ctr Syst Chem, Nijenborgh 4, NL-9747 AG Groningen, Netherlands;‎ European Lab Non Linear Spect LENS, Via N Carrara 1, I-50019 Sesto Fiorentino, Italy; Ist Nazl Ottica, Largo Fermi 6, I-50125 Florence, Italy; Univ Groningen, Univ Med Ctr Groningen, Dept Radiol, Hanzepl 1, NL-9713 GZ Groningen, Netherlands; Radboud Univ Nijmegen, Inst Mol & Mat, FELIX Lab, Toernooiveld 7c, NL-6525 ED Nijmegen, Netherlands

Abstract: Switches that can be actively steered by external stimuli along multiple pathways at the molecular level are the basis for next-generation responsive material systems. The operation of commonly employed molecular photoswitches revolves around one key structural coordinate. Photoswitches with functionalities that depend on and can be addressed along multiple coordinates would offer novel means to tailor and control their behavior and performance. The recently developed donor-acceptor Stenhouse adducts (DASAs) are versatile switches suitable for such applications Their photochemistry is well understood, but is only responsible for part of their overall photoswitching mechanism. The remaining thermal switching pathways are to date unknown. Here, rapid-scan infrared absorption spectroscopy is used to obtain transient fingerprints of reactions occurring on the ground state potential energy surface after reaching structures generated through light absorption. The spectroscopic data are interpreted in terms of structural transformations using kinetic modeling and quantum chemical calculations. Through this combined experimental theoretical approach, we are able to unravel the complexity of the multidimensional ground-state potential energy surface explored by the photoswitch and use this knowledge to predict, and subsequently confirm, how DASA switches can be guided along this potential energy surface. These results break new ground for developing user-geared DASA switches but also shed light on the development of novel photoswitches in general.

Journal/Review: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

Volume: 141 (18)      Pages from: 7376  to: 7384

More Information: This work was supported financially by The Netherlands Organization for Scientific Research (NWO-CW, Top grant to B.L.F., VIDI Grant No. 723.014.001 for W.S., NWO Chemical Innovations Project No. 731.014.209 to W.J.B.), the European Research Council (ERC; Advanced Investigator Grant, No. 694345 to B.L.F.) and the Ministry of Education, Culture and Science (Gravitation program, No. 024.001.035). The computational work was carried out on the Dutch national supercomputer Cartesius with the support of the SURF Cooperative. Furthermore, the authors acknowledge support from Laserlab-Europe (LENS002289, Grant No. 654148) and the Royal Netherlands Academy of Arts and Sciences (KNAW). The Swiss Study Foundation is acknowledged for a fellowship to M.M.L. We thank P. van der Meulen for support with the temperature dependent NMR in situ-irradiation studies and T. Tiemersma-Wegman for ESI-MS analyses.
KeyWords: Visible-light; Photoisomerization; Thermochemistry; Photoswitches
DOI: 10.1021/jacs.9b00341

Citations: 65
data from “WEB OF SCIENCE” (of Thomson Reuters) are update at: 2024-11-17
References taken from IsiWeb of Knowledge: (subscribers only)
Connecting to view paper tab on IsiWeb: Click here
Connecting to view citations from IsiWeb: Click here