Design of a Hole Trapping Ligand

La Croix, Andrew D.; O’Hara, Andrew; Reid, Kemar R.; Orfield, Noah J.; Pantelides, Sokrates T.; Rosenthal, Sandra J.; Macdonald, Janet E.

doi:10.1021/acs.nanolett.6b04213

Title: Design of a Hole Trapping Ligand

Journal Article · Wed Jan 18 00:00:00 EST 2017 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.6b04213· OSTI ID:1340501

;

; Reid, Kemar R.; Orfield, Noah J.; Pantelides, Sokrates T.; Rosenthal, Sandra J.; Macdonald, Janet E.

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

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Research Organization:: Vanderbilt Univ., Nashville, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; FG02-09ER46554; ACI-1053575; EPS-1004083; CHE-1506587

OSTI ID:: 1340501

Journal Information:: Nano Letters, Vol. 17, Issue 2; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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CdSe/CdS nanorod
density functional theory
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Title: Design of a Hole Trapping Ligand

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