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Title: Quantifying the Thermodynamics of Ligand Binding to CsPbBr 3 Quantum Dots

Abstract

We report that 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. 1H NMR methods are 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 an irreversible ligand exchange. Undec-10-en-1-amine exergonically exchanges with oleylamine (K eq = 2.52) at 25 °C. Finally, exchange occurs with carboxylic acids, phosphonic acids, and amines on CsPbBr 3 QDs without etching the nanocrystal surface; increases in steady-state PL intensities are correlated 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) (SC-22)
OSTI Identifier:
1582645
Alternate Identifier(s):
OSTI ID: 1463200
Grant/Contract Number:  
SC0006812; FG02‐11ER46826; 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. doi: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. doi: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 = {We report that 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. 1H NMR methods are used to quantify the thermodynamics of ligand exchange on CsPbBr3 QDs. Both oleic acid and oleylamine native ligands dynamically interact with the CsPbBr3 QD surface, having individual surface densities of 1.2–1.7 nm–2. 10-Undecenoic acid undergoes an exergonic exchange equilibrium with bound oleate (Keq = 1.97) at 25 °C while 10-undecenylphosphonic acid undergoes an irreversible ligand exchange. Undec-10-en-1-amine exergonically exchanges with oleylamine (Keq = 2.52) at 25 °C. Finally, exchange occurs with carboxylic acids, phosphonic acids, and amines on CsPbBr3 QDs without etching the nanocrystal surface; increases in steady-state PL intensities are correlated 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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Cited by: 11 works
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Works referenced in this record:

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    Works referencing / citing this record:

    Self-assembly of a robust hydrogen-bonded octylphosphonate network on cesium lead bromide perovskite nanocrystals for light-emitting diodes
    journal, January 2019

    • Brown, Alasdair A. M.; Hooper, Thomas J. N.; Veldhuis, Sjoerd A.
    • Nanoscale, Vol. 11, Issue 25
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