Carboxylate Anchors Act as Exciton Reporters in 1.3 nm Indium Phosphide Nanoclusters

Joel D. Leger; Max R. Friedfeld; Ryan A. Beck; James D. Gaynor; Alessio Petrone; Xiaosong Li; Brandi M. Cossairt; Munira Khalil

doi:10.1021/acs.jpclett.9b00602

Carboxylate Anchors Act as Exciton Reporters in 1.3 nm Indium Phosphide Nanoclusters

Joel D. Leger, Max R. Friedfeld, Ryan A. Beck, James D. Gaynor, Alessio Petrone, Xiaosong Li, Brandi M. Cossairt, Munira Khalil^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

Developing interfacial probes of ligand-nanocluster interactions is crucial for understanding and tailoring the optoelectronic properties of these emerging nanomaterials. Using transient IR spectroscopy, we demonstrate that ligand vibrational modes of oleate-capped 1.3 nm InP nanoclusters report on the photogenerated exciton. The exciton induces an intensity change in the asymmetric carboxylate stretching mode by 57% while generating no appreciable shift in frequency. Thus, the observed difference signal is attributed to an exciton-induced change in the dipole magnitude of the asymmetric carboxylate stretching mode. Additionally, the transient IR data reveal that the infrared dipole change is dependent on the geometry of the ligand bound to the nanocluster. The experimental results are interpreted using TDDFT calculations, which identify how the spatial dependence of an exciton-induced electron density shift affects the vibrational motion of the carboxylate anchors. More broadly, this work demonstrates transient IR spectroscopy as a useful method for characterizing ligand-nanocluster coupling interactions.

Original language	English (US)
Pages (from-to)	1833-1839
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	10
Issue number	8
DOIs	https://doi.org/10.1021/acs.jpclett.9b00602
State	Published - Apr 18 2019

Funding

M.K. and J.D.L. acknowledge funding from the National Science Foundation (CHE-1565759). B.M.C. acknowledges funding from the National Science Foundation (CHE-1552164). X.L. acknowledges funding from the National Science Foundation (CHE-1565520). M.R.F acknowledges the Washington Research Foundation for fellowship support. J.D.G. is supported by the NSF GRFP, Division of Graduate Education (No. DGE-1256082). R.B. was supported by the University of Washington Molecular Engineering Materials Center funded by the National Science Foundation (DMR-1719797). This work was facilitated by advanced computational, storage, and networking infrastructure provided by the Hyak supercomputer system at the University of Washington, funded by the Student Technology Fee.

ASJC Scopus subject areas

General Materials Science
Physical and Theoretical Chemistry

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10.1021/acs.jpclett.9b00602

Cite this

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title = "Carboxylate Anchors Act as Exciton Reporters in 1.3 nm Indium Phosphide Nanoclusters",

abstract = "Developing interfacial probes of ligand-nanocluster interactions is crucial for understanding and tailoring the optoelectronic properties of these emerging nanomaterials. Using transient IR spectroscopy, we demonstrate that ligand vibrational modes of oleate-capped 1.3 nm InP nanoclusters report on the photogenerated exciton. The exciton induces an intensity change in the asymmetric carboxylate stretching mode by 57% while generating no appreciable shift in frequency. Thus, the observed difference signal is attributed to an exciton-induced change in the dipole magnitude of the asymmetric carboxylate stretching mode. Additionally, the transient IR data reveal that the infrared dipole change is dependent on the geometry of the ligand bound to the nanocluster. The experimental results are interpreted using TDDFT calculations, which identify how the spatial dependence of an exciton-induced electron density shift affects the vibrational motion of the carboxylate anchors. More broadly, this work demonstrates transient IR spectroscopy as a useful method for characterizing ligand-nanocluster coupling interactions.",

author = "Leger, {Joel D.} and Friedfeld, {Max R.} and Beck, {Ryan A.} and Gaynor, {James D.} and Alessio Petrone and Xiaosong Li and Cossairt, {Brandi M.} and Munira Khalil",

note = "Funding Information: M.K. and J.D.L. acknowledge funding from the National Science Foundation (CHE-1565759). B.M.C. acknowledges funding from the National Science Foundation (CHE-1552164). X.L. acknowledges funding from the National Science Foundation (CHE-1565520). M.R.F acknowledges the Washington Research Foundation for fellowship support. J.D.G. is supported by the NSF GRFP, Division of Graduate Education (No. DGE-1256082). R.B. was supported by the University of Washington Molecular Engineering Materials Center funded by the National Science Foundation (DMR-1719797). This work was facilitated by advanced computational, storage, and networking infrastructure provided by the Hyak supercomputer system at the University of Washington, funded by the Student Technology Fee. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

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AU - Leger, Joel D.

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AU - Petrone, Alessio

AU - Li, Xiaosong

AU - Cossairt, Brandi M.

AU - Khalil, Munira

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PY - 2019/4/18

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N2 - Developing interfacial probes of ligand-nanocluster interactions is crucial for understanding and tailoring the optoelectronic properties of these emerging nanomaterials. Using transient IR spectroscopy, we demonstrate that ligand vibrational modes of oleate-capped 1.3 nm InP nanoclusters report on the photogenerated exciton. The exciton induces an intensity change in the asymmetric carboxylate stretching mode by 57% while generating no appreciable shift in frequency. Thus, the observed difference signal is attributed to an exciton-induced change in the dipole magnitude of the asymmetric carboxylate stretching mode. Additionally, the transient IR data reveal that the infrared dipole change is dependent on the geometry of the ligand bound to the nanocluster. The experimental results are interpreted using TDDFT calculations, which identify how the spatial dependence of an exciton-induced electron density shift affects the vibrational motion of the carboxylate anchors. More broadly, this work demonstrates transient IR spectroscopy as a useful method for characterizing ligand-nanocluster coupling interactions.

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Carboxylate Anchors Act as Exciton Reporters in 1.3 nm Indium Phosphide Nanoclusters

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