Quantifying the Thermodynamics of Ligand Binding to CsPbBr 3 Quantum Dots
Abstract
Abstract Cesium lead halide perovskites are an emerging class of quantum dots (QDs) that have shown promise in a variety of applications; however, their properties are highly dependent on their surface chemistry. To this point, the thermodynamics of ligand binding remain unstudied. Herein, 1 H NMR methods were used to quantify the thermodynamics of ligand exchange on CsPbBr 3 QDs. Both oleic acid and oleylamine native ligands dynamically interact with the CsPbBr 3 QD surface, having individual surface densities of 1.2–1.7 nm −2 . 10‐Undecenoic acid undergoes an exergonic exchange equilibrium with bound oleate ( K eq =1.97) at 25 °C while 10‐undecenylphosphonic acid undergoes irreversible ligand exchange. Undec‐10‐en‐1‐amine exergonically exchanges with oleylamine ( K eq =2.52) at 25 °C. Exchange occurs with carboxylic acids, phosphonic acids, and amines on CsPbBr 3 QDs without etching of the nanocrystal surface; increases in the steady‐state PL intensities correlate with more strongly bound conjugate base ligands.
- Authors:
-
[1]
- Department of Chemistry University of Southern California Los Angeles CA 90089 USA
- Department of Chemistry University of Southern California Los Angeles CA 90089 USA, Loker Hydrocarbon Institute University of Southern California Los Angeles CA 90089 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1463201
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 130 Journal Issue: 36; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Smock, Sara R., Williams, Travis J., and Brutchey, Richard L. Quantifying the Thermodynamics of Ligand Binding to CsPbBr 3 Quantum Dots. Germany: N. p., 2018.
Web. doi:10.1002/ange.201806916.
Smock, Sara R., Williams, Travis J., & Brutchey, Richard L. Quantifying the Thermodynamics of Ligand Binding to CsPbBr 3 Quantum Dots. Germany. https://doi.org/10.1002/ange.201806916
Smock, Sara R., Williams, Travis J., and Brutchey, Richard L. Tue .
"Quantifying the Thermodynamics of Ligand Binding to CsPbBr 3 Quantum Dots". Germany. https://doi.org/10.1002/ange.201806916.
@article{osti_1463201,
title = {Quantifying the Thermodynamics of Ligand Binding to CsPbBr 3 Quantum Dots},
author = {Smock, Sara R. and Williams, Travis J. and Brutchey, Richard L.},
abstractNote = {Abstract Cesium lead halide perovskites are an emerging class of quantum dots (QDs) that have shown promise in a variety of applications; however, their properties are highly dependent on their surface chemistry. To this point, the thermodynamics of ligand binding remain unstudied. Herein, 1 H NMR methods were used to quantify the thermodynamics of ligand exchange on CsPbBr 3 QDs. Both oleic acid and oleylamine native ligands dynamically interact with the CsPbBr 3 QD surface, having individual surface densities of 1.2–1.7 nm −2 . 10‐Undecenoic acid undergoes an exergonic exchange equilibrium with bound oleate ( K eq =1.97) at 25 °C while 10‐undecenylphosphonic acid undergoes irreversible ligand exchange. Undec‐10‐en‐1‐amine exergonically exchanges with oleylamine ( K eq =2.52) at 25 °C. Exchange occurs with carboxylic acids, phosphonic acids, and amines on CsPbBr 3 QDs without etching of the nanocrystal surface; increases in the steady‐state PL intensities correlate with more strongly bound conjugate base ligands.},
doi = {10.1002/ange.201806916},
journal = {Angewandte Chemie},
number = 36,
volume = 130,
place = {Germany},
year = {Tue Aug 07 00:00:00 EDT 2018},
month = {Tue Aug 07 00:00:00 EDT 2018}
}
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