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Title: Design of a Hole Trapping Ligand

A new ligand that covalently attaches to the surface of colloidal CdSe/ CdS nanorods and can simultaneously chelate a molecular metal center is described. The dithiocarbamate$-$bipyridine ligand system facilitates hole transfer through energetic overlap at the inorganic$-$organic interface and conjugation through the organic ligand to a chelated metal center. Density functional theory calculations show that the coordination of the free ligand to a CdS surface causes the formation of two hybridized molecular states that lie in the band gap of CdS. The further chelation of Fe(II) to the bipyridine moiety causes the presence of seven midgap states. Hole transfer from the CdS valence band to the midgap states is dipole allowed and occurs at a faster rate than what is experimentally known for the CdSe/CdS band-edge radiative recombination. In the case of the ligand bound with iron, a two-step process emerges that places the hole on the iron, again at rates much faster than band gap recombination. The system was experimentally assembled and characterized via UV$-$vis absorbance spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. Lastly, theoretically predicted red shifts in absorbance were observed experimentally, as well as the expected quench in photoluminescence and lifetimes in time-resolvedmore » photoluminescence« less
Authors:
ORCiD logo ; ORCiD logo ; ; ; ; ;
Publication Date:
Grant/Contract Number:
AC02-05CH11231; FG02-09ER46554; ACI-1053575; EPS-1004083; CHE-1506587
Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 2; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Research Org:
Vanderbilt Univ., Nashville, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; CdSe/CdS nanorod; density functional theory; dithiocarbamate; Hole transfer; midgap states; hole transfer
OSTI Identifier:
1340501
Alternate Identifier(s):
OSTI ID: 1340502; OSTI ID: 1340504

La Croix, Andrew D., O’Hara, Andrew, Reid, Kemar R., Orfield, Noah J., Pantelides, Sokrates T., Rosenthal, Sandra J., and Macdonald, Janet E.. Design of a Hole Trapping Ligand. United States: N. p., Web. doi:10.1021/acs.nanolett.6b04213.
La Croix, Andrew D., O’Hara, Andrew, Reid, Kemar R., Orfield, Noah J., Pantelides, Sokrates T., Rosenthal, Sandra J., & Macdonald, Janet E.. Design of a Hole Trapping Ligand. United States. doi:10.1021/acs.nanolett.6b04213.
La Croix, Andrew D., O’Hara, Andrew, Reid, Kemar R., Orfield, Noah J., Pantelides, Sokrates T., Rosenthal, Sandra J., and Macdonald, Janet E.. 2017. "Design of a Hole Trapping Ligand". United States. doi:10.1021/acs.nanolett.6b04213. https://www.osti.gov/servlets/purl/1340501.
@article{osti_1340501,
title = {Design of a Hole Trapping Ligand},
author = {La Croix, Andrew D. and O’Hara, Andrew and Reid, Kemar R. and Orfield, Noah J. and Pantelides, Sokrates T. and Rosenthal, Sandra J. and Macdonald, Janet E.},
abstractNote = {A new ligand that covalently attaches to the surface of colloidal CdSe/ CdS nanorods and can simultaneously chelate a molecular metal center is described. The dithiocarbamate$-$bipyridine ligand system facilitates hole transfer through energetic overlap at the inorganic$-$organic interface and conjugation through the organic ligand to a chelated metal center. Density functional theory calculations show that the coordination of the free ligand to a CdS surface causes the formation of two hybridized molecular states that lie in the band gap of CdS. The further chelation of Fe(II) to the bipyridine moiety causes the presence of seven midgap states. Hole transfer from the CdS valence band to the midgap states is dipole allowed and occurs at a faster rate than what is experimentally known for the CdSe/CdS band-edge radiative recombination. In the case of the ligand bound with iron, a two-step process emerges that places the hole on the iron, again at rates much faster than band gap recombination. The system was experimentally assembled and characterized via UV$-$vis absorbance spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. Lastly, theoretically predicted red shifts in absorbance were observed experimentally, as well as the expected quench in photoluminescence and lifetimes in time-resolved photoluminescence},
doi = {10.1021/acs.nanolett.6b04213},
journal = {Nano Letters},
number = 2,
volume = 17,
place = {United States},
year = {2017},
month = {1}
}