Jump to main content
Jump to site search

Issue 39, 2018
Previous Article Next Article

Understanding solid-state photoswitching in [Re(OMe2-bpy)(CO)31-NO2)] crystals via in situ photocrystallography

Author affiliations

Abstract

Single-crystal-to-single-crystal nitro → nitrito isomerism is reported for the novel rhenium(I)-bipyridine complex [Re(OMe2-bpy)(CO)31-NO2)], achieving a maximum conversion of 66% to a photoinduced nitrito-(η1-[O with combining low line]NO) isomer under continuous illumination. The 3D X-ray structure of the photoinduced isomer is determined by steady-state and psuedo-steady-state photocrystallographic methods, providing insight into the structural changes required to accommodate photoswitching. Photocrystallographic kinetic studies follow the progress of photoswitching with time, determining a reaction rate constant of k = 0.38(2) min−1 at 150 K. Linkage isomerism is fully-reversible on warming, and pseudo-steady-state experiments confirm that the photoexcited state is retained, at measurable occupancy, up to a temperature of 240 K. These results confirm the validity of combining photoactive linkage isomer and Re(I) photocatalyst chemistries, and the detailed determination of the photoexcited state structure will facilitate the future design of new photoactive Re(I) crystals for a range of applications.

Graphical abstract: Understanding solid-state photoswitching in [Re(OMe2-bpy)(CO)3(η1-NO2)] crystals via in situ photocrystallography

Back to tab navigation

Supplementary files

Publication details

The article was received on 11 May 2018, accepted on 19 Jun 2018 and first published on 19 Jun 2018


Article type: Paper
DOI: 10.1039/C8CE00774H
Citation: CrystEngComm, 2018,20, 5990-5997
  • Open access: Creative Commons BY license
  •   Request permissions

    Understanding solid-state photoswitching in [Re(OMe2-bpy)(CO)31-NO2)] crystals via in situ photocrystallography

    L. E. Hatcher, CrystEngComm, 2018, 20, 5990
    DOI: 10.1039/C8CE00774H

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements