Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies
Indium phosphide quantum dots (QDs) represent promising replacements for more toxic QDs, but InP QD production lags behind other QD materials due to limited understanding of how to tune InP QD growth. We carry out a first-principles, computational screen of the tuning of In carboxylate precursor che...
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| Format: | Article |
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American Chemical Society (ACS)
2020
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| Online Access: | https://hdl.handle.net/1721.1/123831 |
| _version_ | 1811081936144171008 |
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| author | Kim, Jeong Yun Steeves, Adam H. Kulik, Heather Janine |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Kim, Jeong Yun Steeves, Adam H. Kulik, Heather Janine |
| author_sort | Kim, Jeong Yun |
| collection | MIT |
| description | Indium phosphide quantum dots (QDs) represent promising replacements for more toxic QDs, but InP QD production lags behind other QD materials due to limited understanding of how to tune InP QD growth. We carry out a first-principles, computational screen of the tuning of In carboxylate precursor chemistry to alter the kinetics of elementary steps in InP QD growth. We employ a large database normally used for discovery of therapeutic drug-like molecules to discover design rules for these inorganic complexes while maintaining realism (i.e., stable, synthetically accessible substituents) and providing diversity in a 210-molecule test set. We show the In–O bond cleavage energy, which is tuned through ligand functionalization, to be a useful proxy for In–P bond formation energetics in InP QD synthesis. Energy decomposition analysis on a 32-molecule subset reveals that lower activation energies correlate to later transition states, due to stabilization from greater In–P bond formation and more favorable reaction energetics. Our simulations suggest that altering ligand nucleophilicity tunes the reaction barrier over a 10 kcal/mol range, providing the conjugate acid’s pKa as an experimental handle to lead to better control of growth conditions and to improve synthesized InP QD quality. Importantly, these trends hold regardless of phosphorus precursor chemistries and in the longer chain length ligands typically used in synthesis. |
| first_indexed | 2024-09-23T11:54:46Z |
| format | Article |
| id | mit-1721.1/123831 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T11:54:46Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1238312022-10-01T06:56:27Z Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies Kim, Jeong Yun Steeves, Adam H. Kulik, Heather Janine Massachusetts Institute of Technology. Department of Chemical Engineering Indium phosphide quantum dots (QDs) represent promising replacements for more toxic QDs, but InP QD production lags behind other QD materials due to limited understanding of how to tune InP QD growth. We carry out a first-principles, computational screen of the tuning of In carboxylate precursor chemistry to alter the kinetics of elementary steps in InP QD growth. We employ a large database normally used for discovery of therapeutic drug-like molecules to discover design rules for these inorganic complexes while maintaining realism (i.e., stable, synthetically accessible substituents) and providing diversity in a 210-molecule test set. We show the In–O bond cleavage energy, which is tuned through ligand functionalization, to be a useful proxy for In–P bond formation energetics in InP QD synthesis. Energy decomposition analysis on a 32-molecule subset reveals that lower activation energies correlate to later transition states, due to stabilization from greater In–P bond formation and more favorable reaction energetics. Our simulations suggest that altering ligand nucleophilicity tunes the reaction barrier over a 10 kcal/mol range, providing the conjugate acid’s pKa as an experimental handle to lead to better control of growth conditions and to improve synthesized InP QD quality. Importantly, these trends hold regardless of phosphorus precursor chemistries and in the longer chain length ligands typically used in synthesis. National Science Foundation (Grant ECCS-1449291) 2020-02-19T20:34:34Z 2020-02-19T20:34:34Z 2017-04 2017-03 Article http://purl.org/eprint/type/JournalArticle 0897-4756 1520-5002 https://hdl.handle.net/1721.1/123831 Kim, Jeong Yun et al. "Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies." Chemistry of Materials 29, 8 (March 2017): 3632-3643 © 2017 American Chemical Society http://dx.doi.org/10.1021/acs.chemmater.7b00472 Chemistry of Materials Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Kulik |
| spellingShingle | Kim, Jeong Yun Steeves, Adam H. Kulik, Heather Janine Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies |
| title | Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies |
| title_full | Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies |
| title_fullStr | Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies |
| title_full_unstemmed | Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies |
| title_short | Harnessing Organic Ligand Libraries for First-Principles Inorganic Discovery: Indium Phosphide Quantum Dot Precursor Design Strategies |
| title_sort | harnessing organic ligand libraries for first principles inorganic discovery indium phosphide quantum dot precursor design strategies |
| url | https://hdl.handle.net/1721.1/123831 |
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