ArticleJournal of the American Chemical Society2013
Ligand exchange and the stoichiometry of metal chalcogenide nanocrystals: spectroscopic observation of facile metal-carboxylate displacement and binding.
Article in Journal of the American Chemical Society, 2013. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 120 papers.
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Who cites it
120 citing papers in PubMed.
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- Surface Ligands in Nanocrystal Electrocatalysis: A Double-Edged Sword.Advanced materials (Deerfield Beach, Fla.) · 2026Review
- Ligand exchange on nanocrystals: fundamental mechanisms, regulation of nanocrystal properties, self-assembly, and advanced applications.Nanoscale advances · 2026Review
- A Standardized Platform for QLED Fabrication and Characterization.Chemistry of materials : a publication of the American Chemical Society · 2026Article
- In-Situ Ligand-Induced Chirality Transfer in Emissive CdSe Nanoplatelets.The journal of physical chemistry letters · 2026Article
- Precursor Coordination Engineering Enables Epitaxial-Level Carrier Densities in HgTe Colloidal Quantum Dots.Advanced materials (Deerfield Beach, Fla.) · 2026Article
- Dynamic Nuclear Polarization EnhancedThe journal of physical chemistry. C, Nanomaterials and interfaces · 2026Article
- Synthesis, Properties, and Applications of Morphology-Controlled Perovskite Quantum Dots.ACS applied optical materials · 2026Review
- Bright Infrared Colloidal PbS Nanoplatelets with Lead Sulfobromide Shells.Chemistry of materials : a publication of the American Chemical Society · 2026Article
- In-situ entropic ligand engineering enables high-efficiency quantum dot solar cells.Nature communications · 2025Article
- Tribenzoylarsine - A Benign Arsenic Precursor for InAs Nanocrystals.Small (Weinheim an der Bergstrasse, Germany) · 2025Article
- Highly Efficient, Spatially Pure Circularly Polarized Luminescence from Bilayer Self-Assembled Colloidal Quantum Wells and Soft Helical Superstructures.Advanced science (Weinheim, Baden-Wurttemberg, Germany) · 2025Article
- Decoding structural transitions from CdSe nanoclusters to quantum dots through dynamic nuclear polarization NMR.Nature communications · 2025Article
- Prospects of Nanoscience with Nanocrystals: 2025 Edition.ACS nano · 2025Review
- Ligand Exchange and Binding at the Surface of PbS Quantum Dots Quantified Using Multimodal Magnetic Resonance.ACS nano · 2025Article
- Pnictide-based colloidal quantum dots for infrared sensing applications.Nano convergence · 2025Review
- Triplet Sensitization Photon Upconversion Using Near-Infrared Indirect-Bandgap AgBiSJournal of the American Chemical Society · 2025Article
- Silver Telluride Colloidal Quantum Dot Solid for Fast Extended Shortwave Infrared Photodetector.Advanced science (Weinheim, Baden-Wurttemberg, Germany) · 2024Article
- Origin of the High-Frequency Shoulder in the Raman Spectra of CdSe Quantum Dots.The journal of physical chemistry letters · 2024Article
- Ultrathin Boron Growth onto Nanodiamond Surfaces via Electrophilic Boron Precursors.Nanomaterials (Basel, Switzerland) · 2024Article
60 more citing papers are in PubMed but not listed here.
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4 authors.
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Abstract
We demonstrate that metal carboxylate complexes (L-M(O2CR)2, R = oleyl, tetradecyl, M = Cd, Pb) are readily displaced from carboxylate-terminated ME nanocrystals (ME = CdSe, CdS, PbSe, PbS) by various Lewis bases (L = tri-n-butylamine, tetrahydrofuran, tetradecanol, N,N-dimethyl-n-butylamine, tri-n-butylphosphine, N,N,N',N'-tetramethylbutylene-1,4-diamine, pyridine, N,N,N',N'-tetramethylethylene-1,2-diamine, n-octylamine). The relative displacement potency is measured by (1)H NMR spectroscopy and depends most strongly on geometric factors such as sterics and chelation, although also on the hard/soft match with the cadmium ion. The results suggest that ligands displace L-M(O2CR)2 by cooperatively complexing the displaced metal ion as well as the nanocrystal. Removal of up to 90% of surface-bound Cd(O2CR)2 from CdSe and CdS nanocrystals decreases the Cd/Se ratio from 1.1 ± 0.06 to 1.0 ± 0.05, broadens the 1S(e)-2S(3/2h) absorption, and decreases the photoluminescence quantum yield (PLQY) from 10% to <1% (CdSe) and from 20% to <1% (CdS). These changes are partially reversed upon rebinding of M(O2CR)2 at room temperature (∼60%) and fully reversed at elevated temperature. A model is proposed in which electron-accepting M(O2CR)2 complexes (Z-type ligands) reversibly bind to nanocrystals, leading to a range of stoichiometries for a given core size. The results demonstrate that nanocrystals lack a single chemical formula, but are instead dynamic structures with concentration-dependent compositions. The importance of these findings to the synthesis and purification of nanocrystals as well as ligand exchange reactions is discussed.
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