An official website of the United States government
Ligand-exchange reactions of wurtzite CdSe quantum platelets (QPs) and quantum belts (QBs) with methyl viologen (MV2+) and the derivative ligands MV2+(CH2)nNH2 (n = 2, 4, or 6) are investigated. The QP and QB photoluminescence is quenched after partial ligand exchange. Spectroscopic and compositional data establish that this initial ligand substitution occurs on the thin QP and QB edges. The MV2+(CH2)nNH2 ligands are shown to be more-efficient photoluminescence quenchers than the parent MV2+ ion. The ligands on the thin, nonpolar, long-edge facets quench the photoluminescence via the trapping of excitons. Transient absorption experiments indicate the excitons dissociate, and electron transfer to the MV2+(CH2)nNH2 ligands only occurs at the polar, short-edge facets of the wurtzite CdSe QPs and QBs. Electron transfer to the MV2+(CH2)nNH2 ligands occurs within 100 fs when exciting at the band edge and on longer time scales, due to intraband relaxation, when exciting at higher energies.
more »
« less
Bound-Ion Pair X-Type Ligation of Cadmium and Zinc Dithiocarbamates on Cadmium Selenide Quantum Belts
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.
more »
« less
- Award ID(s):
- 1905751
- PAR ID:
- 10484210
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Inorganic Chemistry
- Volume:
- 61
- Issue:
- 15
- ISSN:
- 0020-1669
- Page Range / eLocation ID:
- 5861 to 5868
- Subject(s) / Keyword(s):
- Aromatic compounds,Cadmium selenide, Ligand exchange, Ligands, Ligation
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Neutral metal salts coordinate to the surfaces of colloidal semiconductor nanocrystals (NCs) by acting as Lewis acid acceptors for the NC surface anions. This ligand coordination has been associated with increased emission due to passivation of surface hole traps. Here, variation of the anionic ligands of metal salts is used to study anion effects on metal complex Lewis acidity and surface coordination at CdSe and InP NCs. To resolve dynamic ligand exchange processes, the tetracarbonylcobaltate anion, [Co(CO)4]–, is used as a monoanionic ligand for which IR spectroscopy can readily identify displacement of neutral M[Co(CO)4]x species (M = Cd or In; x = 2 or 3, respectively) upon addition of neutral donor ligands. Notably, although Cd[Co(CO)4]2 is more Lewis acidic than cadmium oleate, the former is more readily displaced from the NC surfaces. Lewis acidity and X-type anion exchange are therefore factors to be considered when performing post-synthetic addition of metal salts for NC photoluminescence emission enhancement.more » « less
-
In a simple, one-step reaction, we have synthesized a pyridoxal-based chemosensor by reacting tris(hydroxymethyl)aminomethane (TRIS) together with pyridoxal hydrochloride to yield a Schiff-base ligand that is highly selective for the detection of Zn( ii ) ion. Both the ligand and the Zn( ii ) complex have been characterized by 1 H & 13 C NMR, ESI-MS, CHN analyses, and X-ray crystallography. The optical properties of the synthesized ligand were investigated in an aqueous buffer solution and found to be highly selective and sensitive toward Zn( ii ) ion through a fluorescence turn-on response. The competition studies reveal the response for zinc ion is unaffected by all alkali and alkaline earth metals; and suppressed by Cu( ii ) ion. The ligand itself shows a weak fluorescence intensity (quantum yield, Φ = 0.04), and the addition of zinc ion enhanced the fluorescence intensity 12-fold (quantum yield, Φ = 0.48). The detection limit for zinc ion was 2.77 × 10 −8 M, which is significantly lower than the WHO's guideline (76.5 μM). Addition of EDTA to a solution containing the ligand–Zn( ii ) complex quenched the fluorescence, indicating the reversibility of Zn( ii ) binding. Stoichiometric studies indicated the formation of a 2 : 1 L 2 Zn complex with a binding constant of 1.2 × 10 9 M −2 (±25%). The crystal structure of the zinc complex shows the same hydrated L 2 Zn complex, with Zn( ii ) ion binding with an octahedral coordination geometry. We also synthesized the copper( ii ) complex of the ligand, and the crystal structure showed the formation of a 1 : 1 adduct, revealing 1-dimensional polymeric networks with octahedral coordinated Cu( ii ). The ligand was employed as a sensor to detect zinc ion in HEK293 cell lines derived from human embryonic kidney cells grown in tissue culture which showed strong luminescence in the presence of Zn( ii ). We believe that the outstanding turn-on response, sensitivity, selectivity, lower detection limit, and reversibility toward zinc ion will find further application in chemical and biological science.more » « less
-
Post-synthetic phase transfer ligand exchange has been established as a simple, reliable, and versatile method for the synthesis of chiral, optically active colloidal nanocrystals displaying circular dichroism (CD) and circularly polarized luminescence (CPL). Herein we present a water-free and purification-free cyclohexane → methanol ligand exchange system that led to the synthesis of stable, non-aggregating chiral and fluorescent cadmium sulfide quantum dots (CdS QDs). Absorption and emission studies revealed that the carboxylate capping ligands can tune the band gap by up to 65 meV as well as control the band gap and deep trap emission pathways. The CD data revealed that the addition of a 2nd stereogenic center did not automatically lead to an increase of the CD anisotropy of QDs, but rather match/mismatch cooperativity effects must be considered in the transfer of the chirality from the capping ligands to the achiral nanocrystals. Variation in position of the functional groups as well as the chemical identity of the functional groups impacted both the shape and anisotropy of the induced CD spectra and revealed the importance of the functional groups’ coordination and polarity on the binding geometry and induced chiroptical properties. Finally, we describe the first example where CD spectra of QDs capped with the same ligand and dissolved in the same solvent displayed very different spectral profiles. This work provides deeper insight into induced CD of QDs and paves the path to rational design of chiral nanomaterials.more » « less
-
The atomic precision of magic-sized clusters offers a route toward narrow emission by eliminating heterogeneous broadening. Herein, we report ultranarrow 467 nm blue emission from cadmium phosphide clusters with a 96 meV line width and as high as 26% photoluminescence quantum yield (PLQY) enabled by tightly bound, bidentate phosphinate ligands. They are obtained through postsynthetic ligand exchange from oleate-capped clusters. The phosphinate maintains the bidentate coordination motif, which does not disturb the metastability of the material but does induce a change in the surface dipole, causing a bathochromic shift in the emission from 457 to 467 nm, which is an optimal wavelength for blue emission. We find that the structure of the ligand tail can heavily influence PLQY and other aspects of the charge carrier dynamics. The ligand exchange protocol can be applied to the related cadmium arsenide clusters, resulting in a narrow 550 nm green emission with a 9% PLQY.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.inorgchem.2c00226
