Probing Solvent-Ligand Interactions in Colloidal Nanocrystals by the NMR Line Broadening

Jonathan De Roo; Nuri Yazdani; Emile Drijvers; Alessandro Lauria; Jorick Maes; Jonathan S. Owen; Isabel Van Driessche; Markus Niederberger; Vanessa Wood; Jose C. Martins; Ivan Infante; Zeger Hens

doi:10.1021/acs.chemmater.8b02523

Probing Solvent-Ligand Interactions in Colloidal Nanocrystals by the NMR Line Broadening

Jonathan De Roo^*, Nuri Yazdani, Emile Drijvers, Alessandro Lauria, Jorick Maes, Jonathan S. Owen, Isabel Van Driessche, Markus Niederberger, Vanessa Wood, Jose C. Martins, Ivan Infante, Zeger Hens

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

Although solvent-ligand interactions play a major role in nanocrystal synthesis, dispersion formulation, and assembly, there is currently no direct method to study this. Here we examine the broadening of ¹H NMR resonances associated with bound ligands and turn this poorly understood descriptor into a tool to assess solvent-ligand interactions. We show that the line broadening has both a homogeneous and a heterogeneous component. The former is nanocrystal-size dependent, and the latter results from solvent-ligand interactions. Our model is supported by experimental and theoretical evidence that correlates broad NMR lines with poor ligand solvation. This correlation is found across a wide range of solvents, extending from water to hexane, for both hydrophobic and hydrophilic ligand types, and for a multitude of oxide, sulfide, and selenide nanocrystals. Our findings thus put forward NMR line-shape analysis as an indispensable tool to form, investigate, and manipulate nanocolloids.

Original language	English
Pages (from-to)	5485-5492
Number of pages	8
Journal	Chemistry of Materials
Volume	30
Issue number	15
Early online date	3 Aug 2018
DOIs	https://doi.org/10.1021/acs.chemmater.8b02523
Publication status	Published - 14 Aug 2018

Funding

The authors acknowledge the FWO Vlaanderen, IWT Vlaanderen, the Belgian American Education Foundation (B.A.E.F.), Fulbright, Ghent University, ETH Zurich, and the COMPASS project (H2020-MSCA-RISE-2015-691185) for financial support. The authors also thank Joep Peters for interesting discussions and suggestions. Brandon McMurtry is acknowledged for help with the TOC graphic.

Funders	Funder number
Belgian American Education Foundation
IWT Vlaanderen
Fulbright Association
Horizon 2020 Framework Programme	691185
Eidgenössische Technische Hochschule Zürich	H2020-MSCA-RISE-2015-691185
Fonds Wetenschappelijk Onderzoek
Universiteit Gent

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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@article{e8d2701c42a84a2988cc2e2d3e76ac82,

title = "Probing Solvent-Ligand Interactions in Colloidal Nanocrystals by the NMR Line Broadening",

abstract = "Although solvent-ligand interactions play a major role in nanocrystal synthesis, dispersion formulation, and assembly, there is currently no direct method to study this. Here we examine the broadening of 1H NMR resonances associated with bound ligands and turn this poorly understood descriptor into a tool to assess solvent-ligand interactions. We show that the line broadening has both a homogeneous and a heterogeneous component. The former is nanocrystal-size dependent, and the latter results from solvent-ligand interactions. Our model is supported by experimental and theoretical evidence that correlates broad NMR lines with poor ligand solvation. This correlation is found across a wide range of solvents, extending from water to hexane, for both hydrophobic and hydrophilic ligand types, and for a multitude of oxide, sulfide, and selenide nanocrystals. Our findings thus put forward NMR line-shape analysis as an indispensable tool to form, investigate, and manipulate nanocolloids.",

author = "{De Roo}, Jonathan and Nuri Yazdani and Emile Drijvers and Alessandro Lauria and Jorick Maes and Owen, {Jonathan S.} and {Van Driessche}, Isabel and Markus Niederberger and Vanessa Wood and Martins, {Jose C.} and Ivan Infante and Zeger Hens",

year = "2018",

month = aug,

day = "14",

doi = "10.1021/acs.chemmater.8b02523",

language = "English",

volume = "30",

pages = "5485--5492",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

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T1 - Probing Solvent-Ligand Interactions in Colloidal Nanocrystals by the NMR Line Broadening

AU - De Roo, Jonathan

AU - Yazdani, Nuri

AU - Drijvers, Emile

AU - Lauria, Alessandro

AU - Maes, Jorick

AU - Owen, Jonathan S.

AU - Van Driessche, Isabel

AU - Niederberger, Markus

AU - Wood, Vanessa

AU - Martins, Jose C.

AU - Infante, Ivan

AU - Hens, Zeger

PY - 2018/8/14

Y1 - 2018/8/14

N2 - Although solvent-ligand interactions play a major role in nanocrystal synthesis, dispersion formulation, and assembly, there is currently no direct method to study this. Here we examine the broadening of 1H NMR resonances associated with bound ligands and turn this poorly understood descriptor into a tool to assess solvent-ligand interactions. We show that the line broadening has both a homogeneous and a heterogeneous component. The former is nanocrystal-size dependent, and the latter results from solvent-ligand interactions. Our model is supported by experimental and theoretical evidence that correlates broad NMR lines with poor ligand solvation. This correlation is found across a wide range of solvents, extending from water to hexane, for both hydrophobic and hydrophilic ligand types, and for a multitude of oxide, sulfide, and selenide nanocrystals. Our findings thus put forward NMR line-shape analysis as an indispensable tool to form, investigate, and manipulate nanocolloids.

AB - Although solvent-ligand interactions play a major role in nanocrystal synthesis, dispersion formulation, and assembly, there is currently no direct method to study this. Here we examine the broadening of 1H NMR resonances associated with bound ligands and turn this poorly understood descriptor into a tool to assess solvent-ligand interactions. We show that the line broadening has both a homogeneous and a heterogeneous component. The former is nanocrystal-size dependent, and the latter results from solvent-ligand interactions. Our model is supported by experimental and theoretical evidence that correlates broad NMR lines with poor ligand solvation. This correlation is found across a wide range of solvents, extending from water to hexane, for both hydrophobic and hydrophilic ligand types, and for a multitude of oxide, sulfide, and selenide nanocrystals. Our findings thus put forward NMR line-shape analysis as an indispensable tool to form, investigate, and manipulate nanocolloids.

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JO - Chemistry of Materials

JF - Chemistry of Materials

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ER -

Probing Solvent-Ligand Interactions in Colloidal Nanocrystals by the NMR Line Broadening

Abstract

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UN SDGs

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