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Bound-Ion Pair X‑Type Ligation of Cadmium and Zinc Dithiocarbamates on Cadmium Selenide Quantum Belts

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journal contribution
posted on 05.04.2022, 20:14 by Hailey M. Meyer, Calynn E. Morrison, Richard A. Loomis, William E. Buhro
Wurtzite CdSe quantum belts with L-type n-octylamine, L-type ammonia, or Z-type Cd­(oleate)2 ligands are exchanged for several metal-dithiocarbamate ligands [M­(S2CNR1R2)2]: Cd­(S2CNPhMe)2, Cd­(S2CNEt2)2, Zn­(S2CNPhMe)2, and Zn­(S2CNEt2)2. Successful ligand exchange with all M­(S2CNR1R2)2 compounds occurs from {CdSe­[Cd­(oleate)2]0.19} quantum belts (QBs), which induce similar spectral shifts in the absorption spectra of the ligand-exchanged QBs. Spectroscopic data, experimentally determined lattice strains, and ligand exchanges with [Na]­[Et2NCS2] and [NH4]­[MePhNCS2] establish that the [M­(S2CNR1R2)2] ligands bind as bound-ion-paired X-type ligands with (S2CNR1R2) groups ligated directly to the QB surfaces and [M­(S2CNR1R2)]+ groups serving as the charge-balancing ion-paired countercations. The X-type dithiocarbamate ligands do not impart any special electronic effects to the CdSe QBs.