Azobenzene-Equipped Covalent Organic Framework: Light-Operated Reservoir

Gobinda Das, Thirumurugan Prakasam, Matthew A. Addicoat, Sudhir Kumar Sharma, Florent Ravaux, Renny Mathew, Maria Baias, Ramesh Jagannathan, Mark A. Olson, Ali Trabolsi

Research output: Contribution to journalArticle

Abstract

Light-operated materials have gained significant attention for their potential technological importance. To achieve molecular motion within extended networks, stimuli-responsive units require free space. The majority of the so far reported 2D-extended organic networks with responsive moieties restrict their freedom of motion on account of their connectivity providing constrained free volume for efficient molecular motion. We report here a light-responsive azobenzene-functionalized covalent organic framework (TTA-AzoDFP) designed in a way that the pendent azobenzene groups are pointing toward the pore channels with sufficient free volume necessary for the unencumbered dynamic motion to occur inside the pores of the covalent organic framework (COF) and undergo a reversible trans-cis photoisomerization upon light irradiation. The resulting hydrophobic COF was used for the storage of rhodamine B and its controlled release in solution by the mechanical motion of the azobenzene units triggered by ultraviolet-light irradiation. The TTA-AzoDFP displayed unprecedented photoregulated fluorescence emission behavior upon UV-light irradiation. Size, emission, and degree of hydrophobicity with respect to trans-cis-trans photoisomerization could be reversibly controlled by alternating UV- and visible-light exposure. The results reported here demonstrate once again the importance of the careful design of the linkers not only to allow the incorporation of molecular switches within the chemical structure of COFs but also to provide the required free space for not hindering their motion. The results demonstrate that responsive COFs could be suitable platforms for delivery systems that can be controlled by external stimuli.

Original languageEnglish (US)
JournalJournal of the American Chemical Society
DOIs
StateAccepted/In press - Jan 1 2019

Fingerprint

Azobenzene
Light
Photoisomerization
rhodamine B
Free volume
Irradiation
Ultraviolet Rays
Hydrophobicity
Ultraviolet radiation
Fluorescence
Switches
Hydrophobic and Hydrophilic Interactions
azobenzene

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Das, G., Prakasam, T., Addicoat, M. A., Sharma, S. K., Ravaux, F., Mathew, R., ... Trabolsi, A. (Accepted/In press). Azobenzene-Equipped Covalent Organic Framework: Light-Operated Reservoir. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b09643

Azobenzene-Equipped Covalent Organic Framework : Light-Operated Reservoir. / Das, Gobinda; Prakasam, Thirumurugan; Addicoat, Matthew A.; Sharma, Sudhir Kumar; Ravaux, Florent; Mathew, Renny; Baias, Maria; Jagannathan, Ramesh; Olson, Mark A.; Trabolsi, Ali.

In: Journal of the American Chemical Society, 01.01.2019.

Research output: Contribution to journalArticle

Das, G, Prakasam, T, Addicoat, MA, Sharma, SK, Ravaux, F, Mathew, R, Baias, M, Jagannathan, R, Olson, MA & Trabolsi, A 2019, 'Azobenzene-Equipped Covalent Organic Framework: Light-Operated Reservoir', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b09643
Das, Gobinda ; Prakasam, Thirumurugan ; Addicoat, Matthew A. ; Sharma, Sudhir Kumar ; Ravaux, Florent ; Mathew, Renny ; Baias, Maria ; Jagannathan, Ramesh ; Olson, Mark A. ; Trabolsi, Ali. / Azobenzene-Equipped Covalent Organic Framework : Light-Operated Reservoir. In: Journal of the American Chemical Society. 2019.
@article{cb8a00c13388445db3fa1c98a8b42fd0,
title = "Azobenzene-Equipped Covalent Organic Framework: Light-Operated Reservoir",
abstract = "Light-operated materials have gained significant attention for their potential technological importance. To achieve molecular motion within extended networks, stimuli-responsive units require free space. The majority of the so far reported 2D-extended organic networks with responsive moieties restrict their freedom of motion on account of their connectivity providing constrained free volume for efficient molecular motion. We report here a light-responsive azobenzene-functionalized covalent organic framework (TTA-AzoDFP) designed in a way that the pendent azobenzene groups are pointing toward the pore channels with sufficient free volume necessary for the unencumbered dynamic motion to occur inside the pores of the covalent organic framework (COF) and undergo a reversible trans-cis photoisomerization upon light irradiation. The resulting hydrophobic COF was used for the storage of rhodamine B and its controlled release in solution by the mechanical motion of the azobenzene units triggered by ultraviolet-light irradiation. The TTA-AzoDFP displayed unprecedented photoregulated fluorescence emission behavior upon UV-light irradiation. Size, emission, and degree of hydrophobicity with respect to trans-cis-trans photoisomerization could be reversibly controlled by alternating UV- and visible-light exposure. The results reported here demonstrate once again the importance of the careful design of the linkers not only to allow the incorporation of molecular switches within the chemical structure of COFs but also to provide the required free space for not hindering their motion. The results demonstrate that responsive COFs could be suitable platforms for delivery systems that can be controlled by external stimuli.",
author = "Gobinda Das and Thirumurugan Prakasam and Addicoat, {Matthew A.} and Sharma, {Sudhir Kumar} and Florent Ravaux and Renny Mathew and Maria Baias and Ramesh Jagannathan and Olson, {Mark A.} and Ali Trabolsi",
year = "2019",
month = "1",
day = "1",
doi = "10.1021/jacs.9b09643",
language = "English (US)",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - Azobenzene-Equipped Covalent Organic Framework

T2 - Light-Operated Reservoir

AU - Das, Gobinda

AU - Prakasam, Thirumurugan

AU - Addicoat, Matthew A.

AU - Sharma, Sudhir Kumar

AU - Ravaux, Florent

AU - Mathew, Renny

AU - Baias, Maria

AU - Jagannathan, Ramesh

AU - Olson, Mark A.

AU - Trabolsi, Ali

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Light-operated materials have gained significant attention for their potential technological importance. To achieve molecular motion within extended networks, stimuli-responsive units require free space. The majority of the so far reported 2D-extended organic networks with responsive moieties restrict their freedom of motion on account of their connectivity providing constrained free volume for efficient molecular motion. We report here a light-responsive azobenzene-functionalized covalent organic framework (TTA-AzoDFP) designed in a way that the pendent azobenzene groups are pointing toward the pore channels with sufficient free volume necessary for the unencumbered dynamic motion to occur inside the pores of the covalent organic framework (COF) and undergo a reversible trans-cis photoisomerization upon light irradiation. The resulting hydrophobic COF was used for the storage of rhodamine B and its controlled release in solution by the mechanical motion of the azobenzene units triggered by ultraviolet-light irradiation. The TTA-AzoDFP displayed unprecedented photoregulated fluorescence emission behavior upon UV-light irradiation. Size, emission, and degree of hydrophobicity with respect to trans-cis-trans photoisomerization could be reversibly controlled by alternating UV- and visible-light exposure. The results reported here demonstrate once again the importance of the careful design of the linkers not only to allow the incorporation of molecular switches within the chemical structure of COFs but also to provide the required free space for not hindering their motion. The results demonstrate that responsive COFs could be suitable platforms for delivery systems that can be controlled by external stimuli.

AB - Light-operated materials have gained significant attention for their potential technological importance. To achieve molecular motion within extended networks, stimuli-responsive units require free space. The majority of the so far reported 2D-extended organic networks with responsive moieties restrict their freedom of motion on account of their connectivity providing constrained free volume for efficient molecular motion. We report here a light-responsive azobenzene-functionalized covalent organic framework (TTA-AzoDFP) designed in a way that the pendent azobenzene groups are pointing toward the pore channels with sufficient free volume necessary for the unencumbered dynamic motion to occur inside the pores of the covalent organic framework (COF) and undergo a reversible trans-cis photoisomerization upon light irradiation. The resulting hydrophobic COF was used for the storage of rhodamine B and its controlled release in solution by the mechanical motion of the azobenzene units triggered by ultraviolet-light irradiation. The TTA-AzoDFP displayed unprecedented photoregulated fluorescence emission behavior upon UV-light irradiation. Size, emission, and degree of hydrophobicity with respect to trans-cis-trans photoisomerization could be reversibly controlled by alternating UV- and visible-light exposure. The results reported here demonstrate once again the importance of the careful design of the linkers not only to allow the incorporation of molecular switches within the chemical structure of COFs but also to provide the required free space for not hindering their motion. The results demonstrate that responsive COFs could be suitable platforms for delivery systems that can be controlled by external stimuli.

UR - http://www.scopus.com/inward/record.url?scp=85075457931&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85075457931&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b09643

DO - 10.1021/jacs.9b09643

M3 - Article

C2 - 31656067

AN - SCOPUS:85075457931

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

ER -