Metal-selenolate chemistry: stereochemistry of adamantane-type clusters of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd)

Recent advances in the chemistry of colloidal semiconductor nanocrystal doping have led to new materials showing fascinating physical properties of potential technological importance. This article provides an overview of efforts to dope one of the most widely studied colloidal semiconductor nanocrystal systems, CdSe quantum dots, with one of the most widely studied transition‐metal dopant ions, Mn2+, and describes the major new physical properties that have emerged following successful synthesis of this material. These properties include spin‐polarizable excitonic photoluminescence, magnetic circular dichroism, exciton storage, and excitonic magnetic polaron formation. A brief survey of parallel advances in the characterization of analogous self‐assembled Mn2+‐doped quantum dots grown by molecular beam epitaxy is also presented, and the physical properties of the colloidal quantum dots are shown to compare favorably with those of the self‐assembled quantum dots. The rich variety of physical properties displayed by colloidal Mn2+‐doped CdSe quantum dots highlights the attractiveness of this material for future fundamental and applied research.

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“…The lower temperature of 10 ] determined by XRD in ref. [139]. Schematic representation showing nanocrystal surface ligation.…”

Section: A Successful Synthesis Of Colloidal Mn 2r :Cdse Nanocrystalsmentioning

confidence: 99%

Mn²⁺‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Beaulac

Archer

Ochsenbein

et al. 2008

Adv Funct Materials

417

463

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“…Adamantane-like anions of the general type [(F-EP~),(MX),]~-are well established for a variety of divalent metal centres, especially for E = S and X = SPh-or halide (1)(2)(3)(4)(5). Of particular relevance to the present paper, some anions of this general type are known for each of the zincgroup elements (1)(2)(3)(4)(5).…”

Section: Introductionmentioning

confidence: 86%

“…Of particular relevance to the present paper, some anions of this general type are known for each of the zincgroup elements (1)(2)(3)(4)(5). The (pSPh),M, cages, where they exist for ~n(11)-H~(II),, provide possible models for the 'Presented in part at the 74th Canadian Chemical Conference, Hamilton, Ontario.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, multinuclear magnetic resonance spectra, and chemistry of some complexes [(μ-SR)₆(MX)₄]²⁻ (R = alkyl; M = Zn or Cd; X = Cl, Br, or I) and the X-ray structural analysis of (Et₄N)₂[(μ-SPrⁱ)₆(CdBr)₄]

Dean¹,

Vittal²,

Wu³

1992

Can. J. Chem.

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. 70,779 (1992). The self-assembly method has been used to prepare a wide range of new adamantane-like anions of the type [(k-SR) (1), and Z = 4. The structure was refined to R(R,,.) = 0.0663(0.0703) with the use of 2669 unique data with I > 2.5u(I). The anion contains an adamantane-type (k,-S),Cd, cage composed of a nearly regular Cd4 tetrahedron and a distorted S6 octahedron, the irregularity of which is caused by 1,3-interactions of the substituent groups on the sulfur atoms. The axial or equatorial dispositions of the six alkyl groups in the four fused M3S3 rings are [aae, aae, aee, aee]. For the zinc-group elements, this is the first example of an adamantane-like (p-Salkyl),M, cage that has been characterized crystallographically.Key words: cadmium complex, cadmium-1 1111 13 NMR, thiolate complex, X-ray analysis, zinc complex.

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“…We have noted that the isomer of [(p-SC6H5)6{HgP-(C6H5),),]+ found in the solid state, isomer 111, is that with the smallest number of 1,3-axial, axial phenyl non-bonded interactions. In an earlier study of related Cd and Zn selenolate complex anions (24), we suggested that the skeleton distorts to minimise the unfavourable repulsive interactions between axially disposed substituents. The presence of bulky triphenylphosphine ligands on the Hg atoms apparently magnifies this distortion.…”

Section: The Synthesis Of the Hg Salt [(P-sc6h5)6{hgp(c6h5)3}mentioning

confidence: 94%

Metal-thiolate chemistry: The structure of the first adamantane-type cation, [(μ-SPh)₆(HgPPh₃)₄]²⁺

Vittal¹,

Dean²,

Payne³

1993

Can. J. Chem.

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The compound [(p-SC6H5)6{HgP(C6H5)3}4][C104]2 crystallizes in the $clinic space group pi as a bis(ch1oroform) solvate with cell dimensions a = 15.799(4), b = 26.813(5), c = 15.040(5) A, a = 96.35(2), P = 114.52(2), y = 100.45(2)" and two formula units per cell. The crystal and molecular structures of this salt were solved by X-ray diffraction techniques using 9898 counter data with I > 2.5a(I) recorded at -50(2)"C. Refinement of 477 variables by full-matrix leastsquares converged at an agreement factor R = 0.046. The cation has adarnantane-type stereochemistry with a (p-SPh)&g, cage and four terminal triphenylphosphine ligands. The S-C, vectors of the bridging SC6H5 groups adopt the configuration [aae, aae, aee, aee] with the minimum number of two 1,3-axial, axial substituent interactions. There is a significant flattening of the two Hg3S, rings with two axial substituents into an envelope conformation; each has two torsion angles less than 25", instead of the ideal values of 260" in adamantane. One perchlorate ion is doubly solvated by chloroform molecules in an unusual, weakly hydrogen bonded, [C104. 2HCC13]-complex.

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Metal-selenolate chemistry: stereochemistry of adamantane-type clusters of formula [(μ-SePh)₆(MSePh)₄]²⁻ (M = Zn and Cd)

Cited by 28 publications

References 16 publications

Mn²⁺‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Mn²⁺‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Synthesis, multinuclear magnetic resonance spectra, and chemistry of some complexes [(μ-SR)₆(MX)₄]²⁻ (R = alkyl; M = Zn or Cd; X = Cl, Br, or I) and the X-ray structural analysis of (Et₄N)₂[(μ-SPrⁱ)₆(CdBr)₄]

Metal-thiolate chemistry: The structure of the first adamantane-type cation, [(μ-SPh)₆(HgPPh₃)₄]²⁺

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Metal-selenolate chemistry: stereochemistry of adamantane-type clusters of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd)

Cited by 28 publications

References 16 publications

Mn2+‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Mn2+‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Synthesis, multinuclear magnetic resonance spectra, and chemistry of some complexes [(μ-SR)6(MX)4]2− (R = alkyl; M = Zn or Cd; X = Cl, Br, or I) and the X-ray structural analysis of (Et4N)2[(μ-SPri)6(CdBr)4]

Metal-thiolate chemistry: The structure of the first adamantane-type cation, [(μ-SPh)6(HgPPh3)4]2+

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Metal-selenolate chemistry: stereochemistry of adamantane-type clusters of formula [(μ-SePh)₆(MSePh)₄]²⁻ (M = Zn and Cd)

Mn²⁺‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Mn²⁺‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Synthesis, multinuclear magnetic resonance spectra, and chemistry of some complexes [(μ-SR)₆(MX)₄]²⁻ (R = alkyl; M = Zn or Cd; X = Cl, Br, or I) and the X-ray structural analysis of (Et₄N)₂[(μ-SPrⁱ)₆(CdBr)₄]

Metal-thiolate chemistry: The structure of the first adamantane-type cation, [(μ-SPh)₆(HgPPh₃)₄]²⁺