Thiol Versus Thiolate Ligation on Cadmium Selenide Quantum Belts

• Published in: Chemistry of materials Vol. 32; no. 1; pp. 205 - 214
• Main Authors: Yao, Yuewei, Buhro, William E
• Format: Journal Article
• Language: English
• Published: American Chemical Society 14-01-2020
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.9b03363

Addition of thiols to semiconductor nanocrystals influences their photoluminescence efficiencies; however, the mode of ligationas neutral thiol ligands or as anionic thiolate ligandsis rarely clearly established. We now differentiate these ligation modes on wurtzite CdSe quantum belts (QBs). n-Dodecanethiol and n-dodecanethiolate ligations of CdSe QBs are obtained through ligand exchanges. Reaction of {CdSe­[Cd­(oleate)2]0.19} QBs and sodium n-dodecanethiolate affords {CdSe­[n-C12H25S]0.23[Na]0.23} QBs, having bound-ion-pair X-type ligation. Reaction of {CdSe­[Cd­(oleate)2]0.19} QBs and n-dodecanethiol affords {CdSe­[Cd­(n-dodecanethiolate)2]0.22} QBs, having Cd­(n-dodecanethiolate)2 ligands as Z-type ligation. {CdSe­[Cd­(n-dodecanethiolate)2]0.22} QBs are also prepared by reaction of {CdSe­[n-octylamine]0.53} QBs and Cd­(n-dodecanethiolate)2. Reaction of {CdSe­[Br]0.1[(n-octyl)4N]0.1} QBs and n-dodecanethiol affords {CdSe­[n-dodecanethiol]0.26} QBs, having L-type ligation. {CdSe­[n-dodecanethiol]0.26} QBs are also prepared by reaction of {CdSe­[n-C12H25S]0.23[Na]0.23} or {CdSe­[Cd­(n-dodecanethiolate)2]0.22} QBs with n-dodecanethiol. Thus, interchange of n-dodecanethiol and n-dodecanethiolate ligation is readily achieved.