Quantifying the Thermodynamics of Ligand Binding to CsPbBr ₃ Quantum Dots

Journal Article · Tue Aug 07 00:00:00 EDT 2018 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201806916· OSTI ID:1463201

Smock, Sara R. ^[1]; Williams, Travis J. ^[2]; Brutchey, Richard L.  ^[1]

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1. Department of Chemistry University of Southern California Los Angeles CA 90089 USA
2. Department of Chemistry University of Southern California Los Angeles CA 90089 USA, Loker Hydrocarbon Institute University of Southern California Los Angeles CA 90089 USA

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.

• Sponsoring Organization: USDOE
• OSTI ID: 1463201
• Journal Information: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 130 Journal Issue: 36; ISSN 0044-8249
• Publisher: Wiley Blackwell (John Wiley & Sons)
• Country of Publication: Germany
• Language: English