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Precision synthesis of a CdSe semiconductor nanocluster via cation exchange

Nature Synthesis volume 2, pages 949–959 (2023)Cite this article

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Abstract

Precision nanosynthesis is essential for atomic engineering in nanostructures and for mechanistic understanding of nanoscale reactions. However, emergent complexity in nanostructures and nanosynthesis makes precision synthesis challenging. Here, we report the precision synthesis of a semiconductor nanocluster via synergizing coordination, cluster and colloidal chemistry at the nanoscale. By using a Cu26Se13(PEt2Ph)14 cluster and a CdI2(PPr3)2 coordination complex as precise precursors in a colloidal cation-exchange reaction, an atomically precise Cd26Se17I18(PPr3)10 (CdSe) cluster is produced at near-unity yield. X-ray crystallography reveals that the child CdSe cluster inherits its icosahedral-packed anion lattice and halide-phosphine-rich surface from the parent cluster and complex, respectively. The hybridization of achiral precursors leads to chiral CdSe clusters cocrystallized as a 1:1 mixture of enantiomers. In situ optical spectroscopy is used to map the precise reaction pathways. On the basis of charge and coordination conservations, the atomic structure of the CdSe cluster can be linked to its synthetic precursors via a series of transformations including surface coordination exchange, intracluster reorganization and intercluster digestive ripening. The precision nanosynthesis described here, with atomically defined precursors, pathways and products, is expected to further facilitate the atomic engineering of functional nanostructures.

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Fig. 1: Cation-exchange reactions across the length scale.
Fig. 2: Precise precursors for cation-exchange reaction and corresponding characterization of precursor and product clusters.
Fig. 3: Cd26Se17I18(PPr3)10 as the precise product of cation exchange.
Fig. 4: Transformation pathways of cation-exchange reaction.

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Data availability

All data are available in the main text or the supplementary information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2221498 for CdI2(PPr3)2, 2221499 for Cd26Se17I18(PPr3)10 and 2221500 for Cu26Se13(PEt2Ph)14. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

We thank I. Ghiviriga and R. Harker for their help in low-temperature NMR characterization. Funding: this research was supported by the University of Florida start-up research funds (C.Z.). We thank the National Science Foundation for funding the X-ray diffractometer through grant no. CHE-1828064 (K.A.A.).

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Florida, Gainesville, FL, USA

    Fuyan Ma, Khalil A. Abboud & Chenjie Zeng

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  1. Fuyan Ma
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Contributions

F.M. and C.Z. conceived and designed the experiments. F.M. synthesized and characterized the materials. K.A.A. and F.M. solved X-ray structures. F.M. and C.Z. wrote the manuscript. C.Z. supervised the project.

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Correspondence to Chenjie Zeng.

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Extended data

Extended Data Fig. 1 Nuclear magnetic resonance (NMR) characterization of the Cu26Se13(PEt2Ph)14 cluster.

a, 31P{H} NMR of free PEt2Ph ligand at room temperature (top) and Cu26Se13(PEt2Ph)14 cluster at variable temperatures (bottom). Seven peaks can be resolved at low-temperature spectra for the cluster, matching with seven chemically inequivalent phosphorous (P1 to P7) in the crystal structure (left). b, Corresponding 1H NMR spectra. c, 1H−1H correlated spectroscopy (COSY) spectrum of the cluster measured at −40 °C (left) and corresponding 1D spectrum (right). Seven groups of correlated protons in the phenyl group of the PEt2Ph ligands can be identified. The sample is measured in toluene-d8. Solvent peaks at 7.09, 6.97-7.01, and 2.08 ppm are labelled by *.

Source data

Extended Data Fig. 2 X-ray crystallographic structure of CdI2(PPr3)2.

a, Unit cell structure. The Cd(II) complexes are presented in the ball-and-stick style while the solvent molecules (toluene) are presented in the stick style. b, Tetrahedron coordination of Cd(II) centre in the individual complex. c, Bond lengths and angles around Cd(II) centre.

Extended Data Fig. 3 Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) characterization of precursor and product clusters.

a, Mass spectrum of Cu26Se13(PEt2Ph)14 cluster and corresponding assignment of fragmentation peaks. All PEt2Ph ligands are dissociated during ionization. The most intense peak is assigned to a dimeric (Cu26Se13)2Cu fragment. b, Mass spectrum of Cd26Se17I18(PPr3)10 cluster and corresponding assignment of fragmentation peaks. The Cd26Se17 cluster framework is dissociated during ionization and reorganized into characteristic fragments of CdSe materials.

Source data

Extended Data Fig. 4 Overview of X-ray crystallographic structure of the Cd26Se17I18(PPr3)10 cluster.

a, Cd26Se17 core, Cd26Se17I18P10 inorganic framework, and Cd26Se17I18(PPr3)10 cluster viewed from three different angles. The corresponding sizes are measured according to the atom-to-atom distance along the edge of the tetrahedron. b, Packing and coordination of Se17 anion lattice (top) and Cd26 cation lattice (bottom). The anion lattice features a central icosahedron capped by four apical Se. The cation lattice can be viewed as four interpenetrating icosahedra. All Se and Cd are tetrahedrally coordinated except for the four apical Se (light yellow). Green: Cd; orange: Se; pink: P; purple: I; grey: C; and white: H.

Extended Data Fig. 5 The overall transformation reaction.

a, the reaction between Cu26Se13(PEt2Ph)14 cluster and CdI2(PPr3)2 complex leads to an atomically precise Cd26Se17I18(PPr3)10 cluster. b, Shell-by-shell structural comparison of the precursors (top) with the product cluster (bottom). c, Comparison of peripheral and radial Se-Se distances of Se13 icosahedral frameworks in Cu26Se13(PEt2Ph)14 (left) and Cd26Se17I18(PPr3)10 (right).

Extended Data Fig. 6 Nuclear magnetic resonance (NMR) characterization of the Cd26Se17I18(PPr3)10 cluster.

a, 31P{1H} NMR spectra of free PPr3 ligand, CdI2(PPr3)2 complex, and Cd26Se17I18(PPr3)10 cluster. A 3:3:3:1 splitting of 10 phosphines is observed for the cluster sample. The satellite peaks observed in both complex and cluster are due to Cd-P couplings. b, Corresponding 1H NMR spectra. c, Amplified 1H NMR spectrum of the cluster at aliphatic region. The four chemically inequivalent phosphines are indicated by numbers (P1 to P4), which matches the C3 symmetry of the structure (left). The sample is measured in CDCl3 at room temperature. The solvent peaks are labelled with *.

Source data

Extended Data Fig. 7 The origin of chirality in Cd26Se17I18(PPr3)10 cluster and the packing of enantiomers in the unit cell.

a, Adaption of tetrahedral coordination into icosahedral framework induces chirality in the core. Left: icosahedral framework in left Cd26Se17 enantiomer with left-leaning Cd-Se bonds along the principal axis. Middle: achiral cuboctahedron in zincblende lattice with vertical alignments of all the Cd-Se bonds. Right: right-leaning Cd-Se bonds in the right Cd26Se17 enantiomer. b, Each unit cell contains two left (dark and light green) and two right (dark and light red) enantiomers. Arrow indicates the direction of the principal C3 axis. The corresponding orientations of enantiomers are shown in the tetrahedral outlines (right). Solvent molecules (toluene) in the unit cell are omitted for clarity.

Extended Data Fig. 8 Symmetry breaking induced by surface ligands.

The uneven distribution of six phosphines (P atom highlighted in yellow) to four corners of the tetrahedron leads to the symmetry breaking from T to C3, with three PPr3 concentrated on the top corner and one PPr3 on each of the base corners of the tetrahedron.

Extended Data Fig. 9 Cation exchange reactions with different CdI2(PR3)2 complexes (R = octyl, butyl, propyl, and ethyl).

The same 365 nm (dark blue curves) and 355 nm (light blue curves) intermediates are observed in reactions with various CdI2(PR3)2 complexes. The reaction with bulkier CdI2[P(octyl)3]2 leads to a slower 355 nm → 372 nm conversion while the reaction with less bulky CdI2(PEt3)2 results in more aggregation. CdI2(PPr3)2 shows the best results in balancing reaction rates and preventing aggregations. In situ UV-vis spectra are monitored every 10 minutes in the first hour (left) and every 2 hours for the rest of the reaction (right).

Source data

Extended Data Fig. 10 Cation exchange reactions with different CdX2(PPr3)2 complexes (X = I−, Br−, Cl−).

Compared to the well-defined 365 nm → 355 nm → 372 nm conversions observed in the CdI2(PPr3)2 reaction, cation exchange using CdBr2(PPr3)2 results in uncontrolled aggregation at the end of the reaction. The aggregation is even faster (within a few minutes) in the case of CdCl2(PPr3)2.

Source data

Supplementary information

Supplementary Information

Supplementary Discussion, Tables 1–3 and Figs. 1–8.

Supplementary Data 1

Crystallographic data for Cu26Se13(PEt2Ph)14.

Supplementary Data 2

Crystallographic data for CdI2(PPr3)2.

Supplementary Data 3

Crystallographic data for Cd26Se17I18(PPr3)10.

Source data

Source Data Fig. 2

UV-vis, powder XRD, 1H NMR, 31P NMR of Cu26 and Cd26 clusters, respectively.

Source Data Fig. 4

In situ UV-vis spectra of the Cu26 to Cd26 conversion.

Source Data Extended Data Fig. 1

NMR spectra of the Cu26 cluster.

Source Data Extended Data Fig. 3

MALDI mass spectra of Cu26 and Cd26 clusters.

Source Data Extended Data Fig. 6

NMR spectra of the Cd26 cluster.

Source Data Extended Data Fig. 9

In situ UV-vis spectra of the cation-exchange reactions with various CdI2(PR3)2 complexes.

Source Data Extended Data Fig. 10

In situ UV-vis spectra of the cation-exchange reactions with various CdX2(PPr3)2 complexes.

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Ma, F., Abboud, K.A. & Zeng, C. Precision synthesis of a CdSe semiconductor nanocluster via cation exchange. Nat. Synth 2, 949–959 (2023). https://doi.org/10.1038/s44160-023-00330-6

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