Designing Janus Ligand Shells on PbS Quantum Dots using Ligand–Ligand Cooperativity

Bronstein, Noah D.; Martinez, Marissa S.; Kroupa, Daniel M.; Vörös, Márton; Lu, Haipeng; Brawand, Nicholas P.; Nozik, Arthur J.; Sellinger, Alan; Galli, Giulia; Beard, Matthew C.

doi:10.1021/acsnano.9b00191

Title: Designing Janus Ligand Shells on PbS Quantum Dots using Ligand–Ligand Cooperativity

Journal Article · Mon Mar 11 00:00:00 EDT 2019 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.9b00191· OSTI ID:1544532

^[1]; Martinez, Marissa S. ^[2]; Kroupa, Daniel M. ^[2];

^[3];

^[1];

^[4];

^[2];

^[5]; Galli, Giulia ^[3];

^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Chicago, IL (United States)
Univ. of Chicago, IL (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)

We present a combined experimental and theoretical study of ligand ligand cooperativity during X-type carboxylate-to-carboxylate ligand exchange reactions on PbS quantum dot surfaces. We find that the ligand dipole moment (varied through changing the substituents on the benzene ring of cinnamic acid derivatives) impacts the ligand-exchange isotherms; in particular, ligands with large electron withdrawing character result in a sharper transition from an oleate-dominated ligand shell to a cinnamate-dominated ligand shell. We developed a two-dimensional lattice model to simulate the ligand-exchange isotherms that accounts for the difference in ligand binding energy as well as ligand ligand cooperativity. Our model shows that ligands with larger ligand ligand coupling energy exhibit sharper isotherms indicating an order disorder phase transition. Lastly, we developed an anisotropic Janus ligand shell by taking advantage of the ligand ligand cooperative ligand exchanges. We monitored the Janus ligand shell using ¹⁹F nuclear magnetic resonance, showing that when the ligand ligand coupling energy falls within the order region of the phase diagram, Janus ligand shells can be constructed.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC36-08GO28308; AC02-06CH11357

OSTI ID:: 1544532

Alternate ID(s):: OSTI ID: 1524451

Report Number(s):: NREL/JA-5900-72996

Journal Information:: ACS Nano, Vol. 13, Issue 4; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 19 works

Citation information provided by
Web of Science

References (33)

Semiconductor Clusters, Nanocrystals, and Quantum Dots Alivisatos, A. P. Science, Vol. 271, Issue 5251, p. 933-937 https://doi.org/10.1126/science.271.5251.933	journal	February 1996
Infrared Quantum Dots: Progress, Challenges, and Opportunities Lu, Haipeng; Carroll, Gerard M.; Neale, Nathan R. ACS Nano https://doi.org/10.1021/acsnano.8b09815	journal	January 2019
Prospects of Nanoscience with Nanocrystals Kovalenko, Maksym V.; Manna, Liberato; Cabot, Andreu ACS Nano, Vol. 9, Issue 2 https://doi.org/10.1021/nn506223h	journal	January 2015
Reaction Chemistry and Ligand Exchange at Cadmium−Selenide Nanocrystal Surfaces Owen, Jonathan S.; Park, Jungwon; Trudeau, Paul-Emile Journal of the American Chemical Society, Vol. 130, Issue 37 https://doi.org/10.1021/ja804414f	journal	September 2008
Synthesis and Micrometer-Scale Assembly of Colloidal CdSe/CdS Nanorods Prepared by a Seeded Growth Approach Carbone, Luigi; Nobile, Concetta; De Giorgi, Milena Nano Letters, Vol. 7, Issue 10 https://doi.org/10.1021/nl0717661	journal	October 2007
Metal Halide Solid-State Surface Treatment for High Efficiency PbS and PbSe QD Solar Cells Crisp, Ryan W.; Kroupa, Daniel M.; Marshall, Ashley R. Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep09945	journal	April 2015
Structural, Optical, and Electrical Properties of Self-Assembled Films of PbSe Nanocrystals Treated with 1,2-Ethanedithiol Luther, Joseph M.; Law, Matt; Song, Qing ACS Nano, Vol. 2, Issue 2 https://doi.org/10.1021/nn7003348	journal	January 2008
PbSe Nanocrystal Solids for n- and p-Channel Thin Film Field-Effect Transistors Talapin, D. V. Science, Vol. 310, Issue 5745, p. 86-89 https://doi.org/10.1126/science.1116703	journal	October 2005
Ligand Exchange and the Stoichiometry of Metal Chalcogenide Nanocrystals: Spectroscopic Observation of Facile Metal-Carboxylate Displacement and Binding Anderson, Nicholas C.; Hendricks, Mark P.; Choi, Joshua J. Journal of the American Chemical Society, Vol. 135, Issue 49, p. 18536-18548 https://doi.org/10.1021/ja4086758	journal	November 2013
A new approach to the formal classification of covalent compounds of the elements Green, M. L. H. Journal of Organometallic Chemistry, Vol. 500, Issue 1-2 https://doi.org/10.1016/0022-328X(95)00508-N	journal	September 1995
The coordination chemistry of nanocrystal surfaces Owen, Jonathan Science, Vol. 347, Issue 6222 https://doi.org/10.1126/science.1259924	journal	February 2015
Ligand-Mediated Interactions between Nanoscale Surfaces Depend Sensitively and Nonlinearly on Temperature, Facet Dimensions, and Ligand Coverage Widmer-Cooper, Asaph; Geissler, Phillip L. ACS Nano, Vol. 10, Issue 2 https://doi.org/10.1021/acsnano.5b05569	journal	January 2016
Ligand-induced twisting of nanoplatelets and their self-assembly into chiral ribbons Jana, Santanu; de Frutos, Marta; Davidson, Patrick Science Advances, Vol. 3, Issue 9 https://doi.org/10.1126/sciadv.1701483	journal	September 2017
Ligand Adsorption/Desorption on Sterically Stabilized InP Colloidal Nanocrystals: Observation and Thermodynamic Analysis Moreels, Iwan; Martins, Jose C.; Hens, Zeger ChemPhysChem, Vol. 7, Issue 5 https://doi.org/10.1002/cphc.200500659	journal	May 2006
“Darker-than-Black” PbS Quantum Dots: Enhancing Optical Absorption of Colloidal Semiconductor Nanocrystals via Short Conjugated Ligands Giansante, Carlo; Infante, Ivan; Fabiano, Eduardo Journal of the American Chemical Society, Vol. 137, Issue 5 https://doi.org/10.1021/ja510739q	journal	January 2015
Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P. The Journal of Physical Chemistry Letters, Vol. 9, Issue 12 https://doi.org/10.1021/acs.jpclett.8b01451	journal	June 2018
Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15257	journal	May 2017
Relaxation of Exciton Confinement in CdSe Quantum Dots by Modification with a Conjugated Dithiocarbamate Ligand Frederick, Matthew T.; Weiss, Emily A. ACS Nano, Vol. 4, Issue 6 https://doi.org/10.1021/nn1007435	journal	May 2010
Electronic Processes within Quantum Dot-Molecule Complexes Harris, Rachel D.; Bettis Homan, Stephanie; Kodaimati, Mohamad Chemical Reviews, Vol. 116, Issue 21 https://doi.org/10.1021/acs.chemrev.6b00102	journal	August 2016
Dependence of the Band Gap of CdSe Quantum Dots on the Surface Coverage and Binding Mode of an Exciton-Delocalizing Ligand, Methylthiophenolate Amin, Victor A.; Aruda, Kenneth O.; Lau, Bryan The Journal of Physical Chemistry C, Vol. 119, Issue 33 https://doi.org/10.1021/acs.jpcc.5b04306	journal	August 2015
Anisotropic particles with patchy, multicompartment and Janus architectures: preparation and application Du, Jianzhong; O'Reilly, Rachel K. Chemical Society Reviews, Vol. 40, Issue 5 https://doi.org/10.1039/c0cs00216j	journal	January 2011
Subnanometre ligand-shell asymmetry leads to Janus-like nanoparticle membranes Jiang, Zhang; He, Jinbo; Deshmukh, Sanket A. Nature Materials, Vol. 14, Issue 9 https://doi.org/10.1038/nmat4321	journal	June 2015
Characterization of Ligand Shell for Mixed-Ligand Coated Gold Nanoparticles Ong, Quy; Luo, Zhi; Stellacci, Francesco Accounts of Chemical Research, Vol. 50, Issue 8 https://doi.org/10.1021/acs.accounts.7b00165	journal	July 2017
Role of Interligand Coupling in Determining the Interfacial Electronic Structure of Colloidal CdS Quantum Dots Harris, Rachel D.; Amin, Victor A.; Lau, Bryan ACS Nano, Vol. 10, Issue 1 https://doi.org/10.1021/acsnano.5b06837	journal	December 2015
A tunable library of substituted thiourea precursors to metal sulfide nanocrystals Hendricks, M. P.; Campos, M. P.; Cleveland, G. T. Science, Vol. 348, Issue 6240 https://doi.org/10.1126/science.aaa2951	journal	June 2015
A survey of Hammett substituent constants and resonance and field parameters Hansch, Corwin.; Leo, A.; Taft, R. W. Chemical Reviews, Vol. 91, Issue 2 https://doi.org/10.1021/cr00002a004	journal	March 1991
Effect of Degree, Type, and Position of Unsaturation on the pKa of Long-Chain Fatty Acids Kanicky, James R.; Shah, Dinesh O. Journal of Colloid and Interface Science, Vol. 256, Issue 1 https://doi.org/10.1006/jcis.2001.8009	journal	December 2002
The Cooperative Molecular Field Effect Cahen, D.; Naaman, R.; Vager, Z. Advanced Functional Materials, Vol. 15, Issue 10 https://doi.org/10.1002/adfm.200500187	journal	October 2005
Calculation of the dielectric constant of monolayer films on a material surface Iwamoto, Mitsumasa; Mizutani, Yoshinobu; Sugimura, Akihiko Physical Review B, Vol. 54, Issue 11 https://doi.org/10.1103/PhysRevB.54.8186	journal	September 1996
Electrostatic charge-charge and dipole-dipole interactions near the surface of a medium with screening non-locality (Review Article) Gabovich, Alexander M.; Voitenko, Alexander I. Low Temperature Physics, Vol. 42, Issue 8 https://doi.org/10.1063/1.4960496	journal	August 2016
Rethinking the term “pi-stacking” Martinez, Chelsea R.; Iverson, Brent L. Chemical Science, Vol. 3, Issue 7 https://doi.org/10.1039/c2sc20045g	journal	January 2012
Determination of monolayer-protected gold nanoparticle ligand–shell morphology using NMR Liu, Xiang; Yu, Miao; Kim, Hyewon Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2155	journal	January 2012
In Situ Observation of Rapid Ligand Exchange in Colloidal Nanocrystal Suspensions Using Transfer NOE Nuclear Magnetic Resonance Spectroscopy Fritzinger, Bernd; Moreels, Iwan; Lommens, Petra Journal of the American Chemical Society, Vol. 131, Issue 8 https://doi.org/10.1021/ja809436y	journal	March 2009

Cited By (1)

Enhanced photoredox activity of CsPbBr ₃ nanocrystals by quantitative colloidal ligand exchange Lu, Haipeng; Zhu, Xiaolin; Miller, Collin The Journal of Chemical Physics, Vol. 151, Issue 20 https://doi.org/10.1063/1.5129261	journal	November 2019

Similar Records

Size-Dependent Janus-Ligand Shell Formation on PbS Quantum Dots

Journal Article · Tue Sep 28 00:00:00 EDT 2021 · Journal of Physical Chemistry. C · OSTI ID:1544532

Martinez, Marissa S.; Nozik, Arthur J.; Beard, Matthew C.

Unsaturated Ligands Seed an Order to Disorder Transition in Mixed Ligand Shells of CdSe/CdS Quantum Dots

Journal Article · Thu Nov 21 00:00:00 EST 2019 · ACS Nano · OSTI ID:1544532

Balan, Arunima D.; Olshansky, Jacob H.; Horowitz, Yonatan; +5 more

Control of Energy Flow Dynamics between Tetracene Ligands and PbS Quantum Dots by Size Tuning and Ligand Coverage

Journal Article · Wed Jan 24 00:00:00 EST 2018 · Nano Letters · OSTI ID:1544532

Kroupa, Daniel M.; Arias, Dylan H.; Blackburn, Jeffrey L.; +5 more

Related Subjects

36 MATERIALS SCIENCE
77 NANOSCIENCE AND NANOTECHNOLOGY
ligand coupling
ligand-QD interactions
PbS quantum dots
QD optical properties
QD surface science
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ligand−QD interactions

Title: Designing Janus Ligand Shells on PbS Quantum Dots using Ligand–Ligand Cooperativity

Citation Formats

References (33)

Cited By (1)

Similar Records

Related Subjects