Cargando…

The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals

[Image: see text] Next-generation colloidal semiconductor nanocrystals featuring enhanced optoelectronic properties and processability are expected to arise from complete mastering of the nanocrystals’ surface characteristics, attained by a rational engineering of the passivating ligands. This aspec...

Descripción completa

Detalles Bibliográficos
Autores principales: Zito, Juliette, Infante, Ivan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8028043/
https://www.ncbi.nlm.nih.gov/pubmed/33635646
http://dx.doi.org/10.1021/acs.accounts.0c00765
_version_ 1783675911059537920
author Zito, Juliette
Infante, Ivan
author_facet Zito, Juliette
Infante, Ivan
author_sort Zito, Juliette
collection PubMed
description [Image: see text] Next-generation colloidal semiconductor nanocrystals featuring enhanced optoelectronic properties and processability are expected to arise from complete mastering of the nanocrystals’ surface characteristics, attained by a rational engineering of the passivating ligands. This aspect is highly challenging, as it underlies a detailed understanding of the critical chemical processes that occur at the nanocrystal–ligand–solvent interface, a task that is prohibitive because of the limited number of nanocrystal syntheses that could be tried in the lab, where only a few dozen of the commercially available starting ligands can actually be explored. However, this challenging goal can be addressed nowadays by combining experiments with atomistic calculations and machine learning algorithms. In the last decades we indeed witnessed major advances in the development and application of computational software dedicated to the solution of the electronic structure problem as well as the expansion of tools to improve the sampling and analysis in classical molecular dynamics simulations. More recently, this progress has also embraced the integration of machine learning in computational chemistry and in the discovery of new drugs. We expect that soon this plethora of computational tools will have a formidable impact also in the field of colloidal semiconductor nanocrystals. In this Account, we present some of the most recent developments in the atomistic description of colloidal nanocrystals. In particular, we show how our group has been developing a set of programs interfaced with available computational chemistry software packages that allow the thermodynamic controlling factors in the nanocrystal surface chemistry to be captured atomistically by including explicit solvent molecules, ligands, and nanocrystal sizes that match the experiments. At the same time, we are also setting up an infrastructure to automate the efficient execution of thousands of calculations that will enable the collection of sufficient data to be processed by machine learning. To fully capture the power of these computational tools in the chemistry of colloidal nanocrystals, we decided to embed the thermodynamics behind the dissolution/precipitation of nanocrystal–ligand complexes in organic solvents and the crucial process of binding/detachment of ligands at the nanocrystal surface into a unique chemical framework. We show that formalizing this mechanism with a computational bird’s eye view helps in deducing the critical factors that govern the stabilization of colloidal dispersions of nanocrystals in an organic solvent as well as the definition of those key parameters that need to be calculated to manipulate surface ligands. This approach has the ultimate goal of engineering surface ligands in silico, anticipating and driving the experiments in the lab.
format Online
Article
Text
id pubmed-8028043
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-80280432021-04-08 The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals Zito, Juliette Infante, Ivan Acc Chem Res [Image: see text] Next-generation colloidal semiconductor nanocrystals featuring enhanced optoelectronic properties and processability are expected to arise from complete mastering of the nanocrystals’ surface characteristics, attained by a rational engineering of the passivating ligands. This aspect is highly challenging, as it underlies a detailed understanding of the critical chemical processes that occur at the nanocrystal–ligand–solvent interface, a task that is prohibitive because of the limited number of nanocrystal syntheses that could be tried in the lab, where only a few dozen of the commercially available starting ligands can actually be explored. However, this challenging goal can be addressed nowadays by combining experiments with atomistic calculations and machine learning algorithms. In the last decades we indeed witnessed major advances in the development and application of computational software dedicated to the solution of the electronic structure problem as well as the expansion of tools to improve the sampling and analysis in classical molecular dynamics simulations. More recently, this progress has also embraced the integration of machine learning in computational chemistry and in the discovery of new drugs. We expect that soon this plethora of computational tools will have a formidable impact also in the field of colloidal semiconductor nanocrystals. In this Account, we present some of the most recent developments in the atomistic description of colloidal nanocrystals. In particular, we show how our group has been developing a set of programs interfaced with available computational chemistry software packages that allow the thermodynamic controlling factors in the nanocrystal surface chemistry to be captured atomistically by including explicit solvent molecules, ligands, and nanocrystal sizes that match the experiments. At the same time, we are also setting up an infrastructure to automate the efficient execution of thousands of calculations that will enable the collection of sufficient data to be processed by machine learning. To fully capture the power of these computational tools in the chemistry of colloidal nanocrystals, we decided to embed the thermodynamics behind the dissolution/precipitation of nanocrystal–ligand complexes in organic solvents and the crucial process of binding/detachment of ligands at the nanocrystal surface into a unique chemical framework. We show that formalizing this mechanism with a computational bird’s eye view helps in deducing the critical factors that govern the stabilization of colloidal dispersions of nanocrystals in an organic solvent as well as the definition of those key parameters that need to be calculated to manipulate surface ligands. This approach has the ultimate goal of engineering surface ligands in silico, anticipating and driving the experiments in the lab. American Chemical Society 2021-02-26 2021-04-06 /pmc/articles/PMC8028043/ /pubmed/33635646 http://dx.doi.org/10.1021/acs.accounts.0c00765 Text en © 2021 The Authors. Published by American Chemical Society Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Zito, Juliette
Infante, Ivan
The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals
title The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals
title_full The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals
title_fullStr The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals
title_full_unstemmed The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals
title_short The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals
title_sort future of ligand engineering in colloidal semiconductor nanocrystals
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8028043/
https://www.ncbi.nlm.nih.gov/pubmed/33635646
http://dx.doi.org/10.1021/acs.accounts.0c00765
work_keys_str_mv AT zitojuliette thefutureofligandengineeringincolloidalsemiconductornanocrystals
AT infanteivan thefutureofligandengineeringincolloidalsemiconductornanocrystals
AT zitojuliette futureofligandengineeringincolloidalsemiconductornanocrystals
AT infanteivan futureofligandengineeringincolloidalsemiconductornanocrystals