Chemistry of Singlet Oxygen with a Cadmium-Sulfur Cluster

Physical Quenching versus Photooxidation

David A. Cagan, Arman C. Garcia, Kin Li, David Ashen-Garry, Abegail C. Tadle, Dong Zhang, Katherine J. Nelms, Yangyang Liu, Jeffrey Shallenberger, Joshua James Stapleton, Matthias Selke

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

We investigated the chemistry of singlet oxygen with a cadmium-sulfur cluster, (Me 4 N) 2 [Cd 4 (SPh) 10 ]. This cluster was used as a model for cadmium-sulfur nanoparticles. Such nanoparticles are often used in conjunction with photosensitizers (for singlet oxygen generation or dye-sensitized solar cells), and hence, it is important to determine if cadmium-sulfur moieties physically quench and/or chemically react with singlet oxygen. We found that (Me 4 N) 2 [Cd 4 (SPh) 10 ] is indeed a very strong quencher of singlet oxygen with total rate constants for 1 O 2 removal of (5.8 ± 1.3) × 10 8 M -1 s -1 in acetonitrile and (1.2 ± 0.5) × 10 8 M -1 s -1 in CD 3 OD. Physical quenching predominates, but chemical reaction leading to decomposition of the cluster and formation of sulfinate is also significant, with a rate constant of (4.1 ± 0.6) × 10 6 M -1 s -1 in methanol. Commercially available cadmium-sulfur quantum dots ("lumidots") show similar singlet oxygen quenching rate constants, based on the molar concentration of the quantum dots.

Original languageEnglish (US)
Pages (from-to)67-71
Number of pages5
JournalJournal of the American Chemical Society
Volume141
Issue number1
DOIs
StatePublished - Jan 9 2019

Fingerprint

Singlet Oxygen
Photooxidation
Cadmium
Sulfur
Quenching
Oxygen
Quantum Dots
Rate constants
Nanoparticles
Semiconductor quantum dots
Photosensitizing Agents
Photosensitizers
Acetonitrile
Methanol
Chemical reactions
Coloring Agents
Decomposition

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Cagan, D. A., Garcia, A. C., Li, K., Ashen-Garry, D., Tadle, A. C., Zhang, D., ... Selke, M. (2019). Chemistry of Singlet Oxygen with a Cadmium-Sulfur Cluster: Physical Quenching versus Photooxidation. Journal of the American Chemical Society, 141(1), 67-71. https://doi.org/10.1021/jacs.8b10516
Cagan, David A. ; Garcia, Arman C. ; Li, Kin ; Ashen-Garry, David ; Tadle, Abegail C. ; Zhang, Dong ; Nelms, Katherine J. ; Liu, Yangyang ; Shallenberger, Jeffrey ; Stapleton, Joshua James ; Selke, Matthias. / Chemistry of Singlet Oxygen with a Cadmium-Sulfur Cluster : Physical Quenching versus Photooxidation. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 1. pp. 67-71.
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Chemistry of Singlet Oxygen with a Cadmium-Sulfur Cluster : Physical Quenching versus Photooxidation. / Cagan, David A.; Garcia, Arman C.; Li, Kin; Ashen-Garry, David; Tadle, Abegail C.; Zhang, Dong; Nelms, Katherine J.; Liu, Yangyang; Shallenberger, Jeffrey; Stapleton, Joshua James; Selke, Matthias.

In: Journal of the American Chemical Society, Vol. 141, No. 1, 09.01.2019, p. 67-71.

Research output: Contribution to journalArticle

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T1 - Chemistry of Singlet Oxygen with a Cadmium-Sulfur Cluster

T2 - Physical Quenching versus Photooxidation

AU - Cagan, David A.

AU - Garcia, Arman C.

AU - Li, Kin

AU - Ashen-Garry, David

AU - Tadle, Abegail C.

AU - Zhang, Dong

AU - Nelms, Katherine J.

AU - Liu, Yangyang

AU - Shallenberger, Jeffrey

AU - Stapleton, Joshua James

AU - Selke, Matthias

PY - 2019/1/9

Y1 - 2019/1/9

N2 - We investigated the chemistry of singlet oxygen with a cadmium-sulfur cluster, (Me 4 N) 2 [Cd 4 (SPh) 10 ]. This cluster was used as a model for cadmium-sulfur nanoparticles. Such nanoparticles are often used in conjunction with photosensitizers (for singlet oxygen generation or dye-sensitized solar cells), and hence, it is important to determine if cadmium-sulfur moieties physically quench and/or chemically react with singlet oxygen. We found that (Me 4 N) 2 [Cd 4 (SPh) 10 ] is indeed a very strong quencher of singlet oxygen with total rate constants for 1 O 2 removal of (5.8 ± 1.3) × 10 8 M -1 s -1 in acetonitrile and (1.2 ± 0.5) × 10 8 M -1 s -1 in CD 3 OD. Physical quenching predominates, but chemical reaction leading to decomposition of the cluster and formation of sulfinate is also significant, with a rate constant of (4.1 ± 0.6) × 10 6 M -1 s -1 in methanol. Commercially available cadmium-sulfur quantum dots ("lumidots") show similar singlet oxygen quenching rate constants, based on the molar concentration of the quantum dots.

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