A 119Sn solid-state nuclear magnetic resonance study of crystalline tin sulphides

Mundus, C.; Taillades, Gilles; Pradel, Annie; Ribes, M.

doi:10.1016/s0926-2040(96)01243-x

Cited by 26 publications

(39 citation statements)

References 19 publications

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“…An analogous NMR spectrum is obtained by combining SnS 2 and K 2 S directly in MFA. Na 6 Sn 2 S 7 has been previously obtained by solid-state synthesis by Krebs et al 37a and characterized with solid-state NMR spectra by Mundus et al 42 A clear spectroscopic signature that distinguishes Sn 2 S 7 6– from Sn 2 S 6 4– is the presence (in good agreement with natural abundances of 117 Sn nuclei) of weaker satellite peaks caused by heteronuclear two bond 119 Sn–S– 117 Sn spin–spin coupling. The 2 J ( 119 Sn, 117 Sn) coupling constant in K 6 Sn 2 S 7 is 349.4 Hz which is in good agreement with literature.…”

Section: Resultsmentioning

confidence: 84%

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

et al. 2015

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Colloidal semiconductor nanocrystals (NCs) are widely studied as building blocks for novel solid-state materials. Inorganic surface functionalization, used to displace native organic capping ligands from NC surfaces, has been a major enabler of electronic solid-state devices based on colloidal NCs. At the same time, very little is known about the atomistic details of the organic-to-inorganic ligand exchange and binding motifs at the NC surface, severely limiting further progress in designing all-inorganic NCs and NC solids. Taking thiostannates (K4SnS4, K4Sn2S6, K6Sn2S7) as typical examples of chalcogenidometallate ligands and oleate-capped CdSe NCs as a model NC system, in this study we address these questions through the combined application of solution 1H NMR spectroscopy, solution and solid-state 119Sn NMR spectroscopy, far-infrared and X-ray absorption spectroscopies, elemental analysis, and by DFT modeling. We show that through the X-type oleate-to-thiostannate ligand exchange, CdSe NCs retain their Cd-rich stoichiometry, with a stoichiometric CdSe core and surface Cd adatoms serving as binding sites for terminal S atoms of the thiostannates ligands, leading to all-inorganic (CdSe)core[Cdm(Sn2S7)yK(6y-2m)]shell (taking Sn2S76– ligand as an example). Thiostannates SnS44– and Sn2S76– retain (distorted) tetrahedral SnS4 geometry upon binding to NC surface. At the same time, experiments and simulations point to lower stability of Sn2S64– (and SnS32–) in most solvents and its lower adaptability to the NC surface caused by rigid Sn2S2 rings.

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Section: Resultsmentioning

confidence: 84%

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

et al. 2015

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“… 51 Furthermore, former studies have shown that the chemical shift tensor parameters of tin sulfides are highly sensitive to coordination numbers and symmetry in the local environment of the tin atom. 52 Therefore, probing the chemical shift anisotropy (CSA) via solid-state NMR provides an opportunity to detect structural details.…”

Section: Results and Discussionmentioning

confidence: 99%

“…This interpretation is supported by earlier findings, which showed that related sharp signals with a lack of prominent sidebands under slow spinning speeds (around 3 kHz) and low magnetic fields correspond to salts containing [SnS 4 ] 4– compounds. 52 The clear contribution of anisotropic chemical shielding (CSA) interactions to the broad signal at −208 ppm indicates a nonisotropic environment of the central tin atom ( Figure 4 a, indicated by a black star). The lower ppm value compared to the sharp peak at 144 ppm suggests the presence of remaining Br atoms because the quadrupolar nature of 79 Br and 81 Br would further contribute to the line broadening.…”

Section: Results and Discussionmentioning

confidence: 99%

Shape Control of Colloidal Cu_2–xS Polyhedral Nanocrystals by Tuning the Nucleation Rates

et al. 2016

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Synthesis protocols for colloidal nanocrystals (NCs) with narrow size and shape distributions are of particular interest for the successful implementation of these nanocrystals into devices. Moreover, the preparation of NCs with well-defined crystal phases is of key importance. In this work, we show that Sn(IV)-thiolate complexes formed in situ strongly influence the nucleation and growth rates of colloidal Cu2–xS polyhedral NCs, thereby dictating their final size, shape, and crystal structure. This allowed us to successfully synthesize hexagonal bifrustums and hexagonal bipyramid NCs with low-chalcocite crystal structure, and hexagonal nanoplatelets with various thicknesses and aspect ratios with the djurleite crystal structure, by solely varying the concentration of Sn(IV)-additives (namely, SnBr4) in the reaction medium. Solution and solid-state 119Sn NMR measurements show that SnBr4 is converted in situ to Sn(IV)–thiolate complexes, which increase the Cu2–xS nucleation barrier without affecting the precursor conversion rates. This influences both the nucleation and growth rates in a concentration-dependent fashion and leads to a better separation between nucleation and growth. Our approach of tuning the nucleation and growth rates with in situ-generated Sn–thiolate complexes might have a more general impact due to the availability of various metal–thiolate complexes, possibly resulting in polyhedral NCs of a wide variety of metal–sulfide compositions.

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“…Wiley-VCH ZAAC 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 The shortest distances for heteronuclear and homonuclear pairs of nuclei reported for the X-ray structure [1] As a third contribution to line broadening, J-couplings have to be taken into account for 119 Sn, since it has been documented previously [9][10][11][12][13][14][15][16][17][18][19][20][21] that they may also be of the order of kHz. In fact, the J-couplings for 119 Sn can be so large that it has been possible to determine the anisotropy of this interaction in some organo-tin compounds [14] by using off-magic angle spinning.…”

Section: Page 4 Of 20mentioning

confidence: 99%

“…Unlike dipolar couplings, which act through space, J-couplings are mediated by covalent bonds, and are difficult to observe in solid-state NMR, because they are usually much smaller than dipolar couplings [6][7][8]. For 119 Sn however, J-couplings tend to be comparatively large (in the range of kHz), and have been reported before in the literature for a variety of compounds [9][10][11][12][13][14][15][16][17][18][19][20][21]. The existence of J-couplings in α-SnF 2 shown here is further evidence for the existence of covalent Sn-F bonds in tin(II) fluoride.…”

Section: Introductionmentioning

confidence: 99%

Covalent Bonds in α‐SnF₂ Monitored by J‐Couplings in Solid‐State NMR Spectra

Bräuniger

Ghedia

Jansen

2010

Zeitschrift anorg allge chemie

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The stable ambient‐temperature phase of tin(II) fluoride, α‐SnF2, was studied by 19F and 119Sn magic‐angle spinning (MAS) NMR spectroscopy. A large chemical shift anisotropy (CSA) is observed in the spectra of both nuclides, which is indicative of the presence of stereochemically active lone electron pair on tin. Symmetric satellite lines with low intensity have been detected in the 119Sn MAS spectra acquired under 19F decoupling, and are assigned to indirect J‐couplings between the magnetically active tin isotopes. The detection of J‐couplings is evidence for the existence of genuine covalent bonds in α‐SnF2, a fact which was deduced before from X‐ray crystallography, which revealed the presence of Sn–F distances smaller than the sum of the respective ionic radii.

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A 119Sn solid-state nuclear magnetic resonance study of crystalline tin sulphides

Cited by 26 publications

References 19 publications

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

Shape Control of Colloidal Cu_2–xS Polyhedral Nanocrystals by Tuning the Nucleation Rates

Covalent Bonds in α‐SnF₂ Monitored by J‐Couplings in Solid‐State NMR Spectra

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A 119Sn solid-state nuclear magnetic resonance study of crystalline tin sulphides

Cited by 26 publications

References 19 publications

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

Shape Control of Colloidal Cu2–xS Polyhedral Nanocrystals by Tuning the Nucleation Rates

Covalent Bonds in α‐SnF2 Monitored by J‐Couplings in Solid‐State NMR Spectra

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Product

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Shape Control of Colloidal Cu_2–xS Polyhedral Nanocrystals by Tuning the Nucleation Rates

Covalent Bonds in α‐SnF₂ Monitored by J‐Couplings in Solid‐State NMR Spectra