{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Protesescu L"],"funding":["European Research Council"],"pagination":["1862-74"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC4525771"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["137(5)"],"pubmed_abstract":["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 (1)H NMR spectroscopy, solution and solid-state (119)Sn 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 Sn2S7(6-) ligand as an example). Thiostannates SnS4(4-) and Sn2S7(6-) retain (distorted) tetrahedral SnS4 geometry upon binding to NC surface. At the same time, experiments and simulations point to lower stability of Sn2S6(4-) (and SnS3(2-)) in most solvents and its lower adaptability to the NC surface caused by rigid Sn2S2 rings."],"journal":["Journal of the American Chemical Society"],"pubmed_title":["Atomistic description of thiostannate-capped CdSe nanocrystals: retention of four-coordinate SnS4 motif and preservation of Cd-rich stoichiometry."],"pmcid":["PMC4525771"],"funding_grant_id":["306733"],"pubmed_authors":["Voznyy O","Kovalenko MV","Rossini AJ","Protesescu L","Emsley L","Coperet C","Gunther D","Sargent EH","Nachtegaal M","Borovinskaya O"],"additional_accession":[]},"is_claimable":false,"name":"Atomistic description of thiostannate-capped CdSe nanocrystals: retention of four-coordinate SnS4 motif and preservation of Cd-rich stoichiometry.","description":"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 (1)H NMR spectroscopy, solution and solid-state (119)Sn 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 Sn2S7(6-) ligand as an example). Thiostannates SnS4(4-) and Sn2S7(6-) retain (distorted) tetrahedral SnS4 geometry upon binding to NC surface. At the same time, experiments and simulations point to lower stability of Sn2S6(4-) (and SnS3(2-)) in most solvents and its lower adaptability to the NC surface caused by rigid Sn2S2 rings.","dates":{"release":"2015-01-01T00:00:00Z","publication":"2015 Feb","modification":"2021-03-17T08:02:32Z","creation":"2019-03-27T01:56:18Z"},"accession":"S-EPMC4525771","cross_references":{"pubmed":["25597625"],"doi":["10.1021/ja510862c"]}}