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Title: Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 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];  [2]; ORCiD logo [1]
  1. Univ. of Southern California, Los Angeles, CA (United States)
  2. Univ. of Southern California, Los Angeles, CA (United States). Loker Hydrocarbon Inst.
Publication Date:
Research Org.:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1582645
Alternate Identifier(s):
OSTI ID: 1463200
Grant/Contract Number:  
SC0006812; FG02‐11ER46826
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 36; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CsPbBr3; ligands; NMR spectroscopy; perovskites; quantum dots

Citation Formats

Smock, Sara R., Williams, Travis J., and Brutchey, Richard L. Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots. United States: N. p., 2018. Web. doi:10.1002/anie.201806916.
Smock, Sara R., Williams, Travis J., & Brutchey, Richard L. Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots. United States. https://doi.org/10.1002/anie.201806916
Smock, Sara R., Williams, Travis J., and Brutchey, Richard L. Thu . "Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots". United States. https://doi.org/10.1002/anie.201806916. https://www.osti.gov/servlets/purl/1582645.
@article{osti_1582645,
title = {Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 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/anie.201806916},
journal = {Angewandte Chemie (International Edition)},
number = 36,
volume = 57,
place = {United States},
year = {2018},
month = {7}
}

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