Control of the Redox Activity of Quantum Dots through Introduction of Fluoroalkanethiolates into Their Ligand Shells

David J. Weinberg, Chen He, Emily A Weiss

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Increasing the fraction of 1H,1H,2H,2H-perfluorodecanethiol (PFDT) in the mixed-PFDT/oleate ligand shell of a PbS quantum dot (QD) dramatically reduces the permeability of the ligand shell to alkyl-substituted benzoquinones (s-BQs), as measured by a decrease in the efficiency of collisional photoinduced electron transfer. Replacing only 21% of the oleates on the QD surface with PFDT reduces the yield of photo-oxidation by tetramethyl BQ by 68%. Experiments with s-BQ quenchers of two different sizes reveal that the degree of protection provided by the PFDT-doped monolayer, relative to a decanethiolate (DT)-doped monolayer at similar coverage, is due to both size exclusion (PFDT is larger and more rigid than DT), and the oleophobicity of PFDT. This work demonstrates the usefulness of fluorinated ligands in designing molecule-selective and potentially corrosion-inhibiting surface coatings for QDs for applications as robust emitters or high fidelity sensing platforms.

Original languageEnglish
Pages (from-to)2319-2326
Number of pages8
JournalJournal of the American Chemical Society
Volume138
Issue number7
DOIs
Publication statusPublished - Mar 2 2016

Fingerprint

Quantum Dots
Benzoquinones
Semiconductor quantum dots
Oxidation-Reduction
Ligands
Monolayers
Corrosion
Photooxidation
Oleic Acid
Permeability
Electrons
Coatings
Molecules
Experiments

ASJC Scopus subject areas

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

Cite this

Control of the Redox Activity of Quantum Dots through Introduction of Fluoroalkanethiolates into Their Ligand Shells. / Weinberg, David J.; He, Chen; Weiss, Emily A.

In: Journal of the American Chemical Society, Vol. 138, No. 7, 02.03.2016, p. 2319-2326.

Research output: Contribution to journalArticle

@article{d905927b88964ff58cf5fcb60a6d599b,
title = "Control of the Redox Activity of Quantum Dots through Introduction of Fluoroalkanethiolates into Their Ligand Shells",
abstract = "Increasing the fraction of 1H,1H,2H,2H-perfluorodecanethiol (PFDT) in the mixed-PFDT/oleate ligand shell of a PbS quantum dot (QD) dramatically reduces the permeability of the ligand shell to alkyl-substituted benzoquinones (s-BQs), as measured by a decrease in the efficiency of collisional photoinduced electron transfer. Replacing only 21{\%} of the oleates on the QD surface with PFDT reduces the yield of photo-oxidation by tetramethyl BQ by 68{\%}. Experiments with s-BQ quenchers of two different sizes reveal that the degree of protection provided by the PFDT-doped monolayer, relative to a decanethiolate (DT)-doped monolayer at similar coverage, is due to both size exclusion (PFDT is larger and more rigid than DT), and the oleophobicity of PFDT. This work demonstrates the usefulness of fluorinated ligands in designing molecule-selective and potentially corrosion-inhibiting surface coatings for QDs for applications as robust emitters or high fidelity sensing platforms.",
author = "Weinberg, {David J.} and Chen He and Weiss, {Emily A}",
year = "2016",
month = "3",
day = "2",
doi = "10.1021/jacs.5b13077",
language = "English",
volume = "138",
pages = "2319--2326",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "7",

}

TY - JOUR

T1 - Control of the Redox Activity of Quantum Dots through Introduction of Fluoroalkanethiolates into Their Ligand Shells

AU - Weinberg, David J.

AU - He, Chen

AU - Weiss, Emily A

PY - 2016/3/2

Y1 - 2016/3/2

N2 - Increasing the fraction of 1H,1H,2H,2H-perfluorodecanethiol (PFDT) in the mixed-PFDT/oleate ligand shell of a PbS quantum dot (QD) dramatically reduces the permeability of the ligand shell to alkyl-substituted benzoquinones (s-BQs), as measured by a decrease in the efficiency of collisional photoinduced electron transfer. Replacing only 21% of the oleates on the QD surface with PFDT reduces the yield of photo-oxidation by tetramethyl BQ by 68%. Experiments with s-BQ quenchers of two different sizes reveal that the degree of protection provided by the PFDT-doped monolayer, relative to a decanethiolate (DT)-doped monolayer at similar coverage, is due to both size exclusion (PFDT is larger and more rigid than DT), and the oleophobicity of PFDT. This work demonstrates the usefulness of fluorinated ligands in designing molecule-selective and potentially corrosion-inhibiting surface coatings for QDs for applications as robust emitters or high fidelity sensing platforms.

AB - Increasing the fraction of 1H,1H,2H,2H-perfluorodecanethiol (PFDT) in the mixed-PFDT/oleate ligand shell of a PbS quantum dot (QD) dramatically reduces the permeability of the ligand shell to alkyl-substituted benzoquinones (s-BQs), as measured by a decrease in the efficiency of collisional photoinduced electron transfer. Replacing only 21% of the oleates on the QD surface with PFDT reduces the yield of photo-oxidation by tetramethyl BQ by 68%. Experiments with s-BQ quenchers of two different sizes reveal that the degree of protection provided by the PFDT-doped monolayer, relative to a decanethiolate (DT)-doped monolayer at similar coverage, is due to both size exclusion (PFDT is larger and more rigid than DT), and the oleophobicity of PFDT. This work demonstrates the usefulness of fluorinated ligands in designing molecule-selective and potentially corrosion-inhibiting surface coatings for QDs for applications as robust emitters or high fidelity sensing platforms.

UR - http://www.scopus.com/inward/record.url?scp=84959378359&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84959378359&partnerID=8YFLogxK

U2 - 10.1021/jacs.5b13077

DO - 10.1021/jacs.5b13077

M3 - Article

AN - SCOPUS:84959378359

VL - 138

SP - 2319

EP - 2326

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 7

ER -