Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots

Smock, Sara R.; Williams, Travis J.; Brutchey, Richard L.

doi:10.1002/anie.201806916

Quantifying the Thermodynamics of Ligand Binding to CsPbBr₃ Quantum Dots

Journal Article · Thu Jul 26 00:00:00 EDT 2018 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201806916· OSTI ID:1582645

Smock, Sara R. ^[1]; Williams, Travis J. ^[2]; ^[3]

Univ. of Southern California, Los Angeles, CA (United States); University of Southern California
Univ. of Southern California, Los Angeles, CA (United States). Loker Hydrocarbon Inst.
Univ. of Southern California, Los Angeles, CA (United States)

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 (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 CsPbBr₃ QDs without etching the nanocrystal surface; increases in steady-state PL intensities are correlated with more strongly bound conjugate base ligands.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0006812; SC0006812

OSTI ID:: 1582645

Alternate ID(s):: OSTI ID: 22733712
OSTI ID: 1463200

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 36 Vol. 57; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Quantifying the Thermodynamics of Ligand Binding to CsPbBr ₃ Quantum Dots

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CsPbBr3
NMR spectroscopy
ligands
perovskites
quantum dots