TY - JOUR
T1 - Photomodulation of fluoride ion binding through anion-φ interactions using a photoswitchable azobenzene system
AU - Rananaware, Anushri
AU - Samanta, Mousumi
AU - Bhosale, Rajesh S.
AU - Kobaisi, Mohammad Al
AU - Roy, Biswajit
AU - Bheemireddy, Varun
AU - Bhosale, Sidhanath V.
AU - Bandyopadhyay, Subhajit
AU - Bhosale, Sheshanath V.
N1 - Funding Information:
This work was financially support by the Australian Research Council under a Future Fellowship Scheme (FT110100152). S.B. acknowledges DST, India for financial support under Grant # SR/S1/OC-26/2010, and S.V.B. (IICT) is grateful for financial support from the SERB (SB/S1/IC-09/2014), New Delhi, India and Intelcoat project CSC0114, CSIR, New Delhi, India. R.S.B. acknowledges financial support from CSIR, New Delhi under the SRA scheme [13(8772)-A)/2015-Pool].
PY - 2016/3/8
Y1 - 2016/3/8
N2 - The discovery of photoswitchable azobenzene-systems that undergo trans-to-cis photoisomerisation was a milestone in supramolecular chemistry. Such photoswitches have possible applications in data storage, stimuli responsive delivery systems, and molecular machines due to fast and selective switching. However, the light induced cis isomer of azobenzene is rather unstable and reverts thermally and photochemically to the thermodynamically stable trans configuration. We report, for the first time, controlled photoswitching of an azo-naphthalenediimide (azo-NDI) which can be achieved upon binding of fluoride ions through anion-φ interaction. This NDI-F-NDI "sandwich' stabilises the cis configuration through the generation of an NDI-radical anion, and a dianionic, NDI 2- species that becomes unusually stable in the cis form. The sandwiched cis form reverts to the trans form only upon decomplexation of F -. A model pollutant was successfully degraded using the photogenerated NDI-F-NDI sandwich. This opens a wide range of applications in molecular and supramolecular nanotechnology.
AB - The discovery of photoswitchable azobenzene-systems that undergo trans-to-cis photoisomerisation was a milestone in supramolecular chemistry. Such photoswitches have possible applications in data storage, stimuli responsive delivery systems, and molecular machines due to fast and selective switching. However, the light induced cis isomer of azobenzene is rather unstable and reverts thermally and photochemically to the thermodynamically stable trans configuration. We report, for the first time, controlled photoswitching of an azo-naphthalenediimide (azo-NDI) which can be achieved upon binding of fluoride ions through anion-φ interaction. This NDI-F-NDI "sandwich' stabilises the cis configuration through the generation of an NDI-radical anion, and a dianionic, NDI 2- species that becomes unusually stable in the cis form. The sandwiched cis form reverts to the trans form only upon decomplexation of F -. A model pollutant was successfully degraded using the photogenerated NDI-F-NDI sandwich. This opens a wide range of applications in molecular and supramolecular nanotechnology.
UR - http://www.scopus.com/inward/record.url?scp=84960510555&partnerID=8YFLogxK
U2 - 10.1038/srep22928
DO - 10.1038/srep22928
M3 - Article
AN - SCOPUS:84960510555
SN - 2045-2322
VL - 6
JO - Scientific Reports
JF - Scientific Reports
M1 - 22928
ER -