Redox-Responsive Covalent Organic Nanosheets from Viologens and Calix[4]arene for Iodine and Toxic Dye Capture

Tina Skorjanc, Dinesh Shetty, Sudhir Kumar Sharma, Jesus Raya, Hassan Traboulsi, Dong Suk Han, Jayesh Lalla, Ryan Newlon, Ramesh Jagannathan, Serdal Kirmizialtin, John Carl Olsen, Ali Trabolsi

Research output: Contribution to journalArticle

Abstract

Owing to their chemical and thermal stabilities, high uptake capacities, and easy recyclability, covalent organic polymers (COPs) have shown promise as pollutant sponges. Herein, we describe the use of diazo coupling to synthesize two cationic COPs, COP1++ and COP2++, that incorporate a viologen-based molecular switch and an organic macrocycle, calix[4]arene. The COPs form nanosheets that have height profiles of 6.00 nm and 8.00 nm, respectively, based on AFM measurements. The sheets remain morphologically intact upon one- or two-electron reductions of their viologen subunits. MD simulations of the COPs containing dicationic viologens indicate that the calix[4]arenes adopt a partial cone conformation and that, in height, the individual 2D polymer layers are 5.48 Å in COP1++ and 5.65 Å in COP2++, which, together with the AFM measurements, suggests that the nanosheets are composed of 11 and 14 layers, respectively. Whether their viologens are in dicationic, radical cationic, or neutral form, the COPs exhibit high affinity for iodine, reaching up to 200 % mass increase when exposed to iodine vapor at 70 °C, which makes the materials among the best-performing nanosheets for iodine capture reported in the literature. In addition, the COPs effectively remove Congo red from solution in the pH range of 2–10, reaching nearly 100 % removal within 15 minutes at acidic pH.

Original languageEnglish (US)
Pages (from-to)8648-8655
Number of pages8
JournalChemistry - A European Journal
Volume24
Issue number34
DOIs
StatePublished - Jun 18 2018

Fingerprint

Viologens
Organic polymers
Nanosheets
Poisons
Iodine
Coloring Agents
Dyes
Congo Red
Electrons
Chemical stability
Conformations
calix(4)arene
Oxidation-Reduction
Cones
Polymers
Thermodynamic stability
Vapors
Switches

Keywords

  • calix[4]arenes
  • Congo red
  • iodine capture
  • nanosheets
  • viologen

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Redox-Responsive Covalent Organic Nanosheets from Viologens and Calix[4]arene for Iodine and Toxic Dye Capture. / Skorjanc, Tina; Shetty, Dinesh; Sharma, Sudhir Kumar; Raya, Jesus; Traboulsi, Hassan; Han, Dong Suk; Lalla, Jayesh; Newlon, Ryan; Jagannathan, Ramesh; Kirmizialtin, Serdal; Olsen, John Carl; Trabolsi, Ali.

In: Chemistry - A European Journal, Vol. 24, No. 34, 18.06.2018, p. 8648-8655.

Research output: Contribution to journalArticle

Skorjanc, Tina ; Shetty, Dinesh ; Sharma, Sudhir Kumar ; Raya, Jesus ; Traboulsi, Hassan ; Han, Dong Suk ; Lalla, Jayesh ; Newlon, Ryan ; Jagannathan, Ramesh ; Kirmizialtin, Serdal ; Olsen, John Carl ; Trabolsi, Ali. / Redox-Responsive Covalent Organic Nanosheets from Viologens and Calix[4]arene for Iodine and Toxic Dye Capture. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 34. pp. 8648-8655.
@article{f8d62c5c3df24f6aa91a89f7a7fedd01,
title = "Redox-Responsive Covalent Organic Nanosheets from Viologens and Calix[4]arene for Iodine and Toxic Dye Capture",
abstract = "Owing to their chemical and thermal stabilities, high uptake capacities, and easy recyclability, covalent organic polymers (COPs) have shown promise as pollutant sponges. Herein, we describe the use of diazo coupling to synthesize two cationic COPs, COP1++ and COP2++, that incorporate a viologen-based molecular switch and an organic macrocycle, calix[4]arene. The COPs form nanosheets that have height profiles of 6.00 nm and 8.00 nm, respectively, based on AFM measurements. The sheets remain morphologically intact upon one- or two-electron reductions of their viologen subunits. MD simulations of the COPs containing dicationic viologens indicate that the calix[4]arenes adopt a partial cone conformation and that, in height, the individual 2D polymer layers are 5.48 {\AA} in COP1++ and 5.65 {\AA} in COP2++, which, together with the AFM measurements, suggests that the nanosheets are composed of 11 and 14 layers, respectively. Whether their viologens are in dicationic, radical cationic, or neutral form, the COPs exhibit high affinity for iodine, reaching up to 200 {\%} mass increase when exposed to iodine vapor at 70 °C, which makes the materials among the best-performing nanosheets for iodine capture reported in the literature. In addition, the COPs effectively remove Congo red from solution in the pH range of 2–10, reaching nearly 100 {\%} removal within 15 minutes at acidic pH.",
keywords = "calix[4]arenes, Congo red, iodine capture, nanosheets, viologen",
author = "Tina Skorjanc and Dinesh Shetty and Sharma, {Sudhir Kumar} and Jesus Raya and Hassan Traboulsi and Han, {Dong Suk} and Jayesh Lalla and Ryan Newlon and Ramesh Jagannathan and Serdal Kirmizialtin and Olsen, {John Carl} and Ali Trabolsi",
year = "2018",
month = "6",
day = "18",
doi = "10.1002/chem.201800623",
language = "English (US)",
volume = "24",
pages = "8648--8655",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "34",

}

TY - JOUR

T1 - Redox-Responsive Covalent Organic Nanosheets from Viologens and Calix[4]arene for Iodine and Toxic Dye Capture

AU - Skorjanc, Tina

AU - Shetty, Dinesh

AU - Sharma, Sudhir Kumar

AU - Raya, Jesus

AU - Traboulsi, Hassan

AU - Han, Dong Suk

AU - Lalla, Jayesh

AU - Newlon, Ryan

AU - Jagannathan, Ramesh

AU - Kirmizialtin, Serdal

AU - Olsen, John Carl

AU - Trabolsi, Ali

PY - 2018/6/18

Y1 - 2018/6/18

N2 - Owing to their chemical and thermal stabilities, high uptake capacities, and easy recyclability, covalent organic polymers (COPs) have shown promise as pollutant sponges. Herein, we describe the use of diazo coupling to synthesize two cationic COPs, COP1++ and COP2++, that incorporate a viologen-based molecular switch and an organic macrocycle, calix[4]arene. The COPs form nanosheets that have height profiles of 6.00 nm and 8.00 nm, respectively, based on AFM measurements. The sheets remain morphologically intact upon one- or two-electron reductions of their viologen subunits. MD simulations of the COPs containing dicationic viologens indicate that the calix[4]arenes adopt a partial cone conformation and that, in height, the individual 2D polymer layers are 5.48 Å in COP1++ and 5.65 Å in COP2++, which, together with the AFM measurements, suggests that the nanosheets are composed of 11 and 14 layers, respectively. Whether their viologens are in dicationic, radical cationic, or neutral form, the COPs exhibit high affinity for iodine, reaching up to 200 % mass increase when exposed to iodine vapor at 70 °C, which makes the materials among the best-performing nanosheets for iodine capture reported in the literature. In addition, the COPs effectively remove Congo red from solution in the pH range of 2–10, reaching nearly 100 % removal within 15 minutes at acidic pH.

AB - Owing to their chemical and thermal stabilities, high uptake capacities, and easy recyclability, covalent organic polymers (COPs) have shown promise as pollutant sponges. Herein, we describe the use of diazo coupling to synthesize two cationic COPs, COP1++ and COP2++, that incorporate a viologen-based molecular switch and an organic macrocycle, calix[4]arene. The COPs form nanosheets that have height profiles of 6.00 nm and 8.00 nm, respectively, based on AFM measurements. The sheets remain morphologically intact upon one- or two-electron reductions of their viologen subunits. MD simulations of the COPs containing dicationic viologens indicate that the calix[4]arenes adopt a partial cone conformation and that, in height, the individual 2D polymer layers are 5.48 Å in COP1++ and 5.65 Å in COP2++, which, together with the AFM measurements, suggests that the nanosheets are composed of 11 and 14 layers, respectively. Whether their viologens are in dicationic, radical cationic, or neutral form, the COPs exhibit high affinity for iodine, reaching up to 200 % mass increase when exposed to iodine vapor at 70 °C, which makes the materials among the best-performing nanosheets for iodine capture reported in the literature. In addition, the COPs effectively remove Congo red from solution in the pH range of 2–10, reaching nearly 100 % removal within 15 minutes at acidic pH.

KW - calix[4]arenes

KW - Congo red

KW - iodine capture

KW - nanosheets

KW - viologen

UR - http://www.scopus.com/inward/record.url?scp=85048777738&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85048777738&partnerID=8YFLogxK

U2 - 10.1002/chem.201800623

DO - 10.1002/chem.201800623

M3 - Article

VL - 24

SP - 8648

EP - 8655

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 34

ER -